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WO2012002370A1 - Composition formant une résine de polyuréthanne et produit d'étanchéité - Google Patents

Composition formant une résine de polyuréthanne et produit d'étanchéité Download PDF

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Publication number
WO2012002370A1
WO2012002370A1 PCT/JP2011/064776 JP2011064776W WO2012002370A1 WO 2012002370 A1 WO2012002370 A1 WO 2012002370A1 JP 2011064776 W JP2011064776 W JP 2011064776W WO 2012002370 A1 WO2012002370 A1 WO 2012002370A1
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WO
WIPO (PCT)
Prior art keywords
polyurethane resin
forming composition
castor oil
isocyanate
group
Prior art date
Application number
PCT/JP2011/064776
Other languages
English (en)
Japanese (ja)
Inventor
将司 金谷
沙織 山口
功二 大和
Original Assignee
日本ポリウレタン工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本ポリウレタン工業株式会社 filed Critical 日本ポリウレタン工業株式会社
Priority to JP2012522636A priority Critical patent/JP5489028B2/ja
Publication of WO2012002370A1 publication Critical patent/WO2012002370A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/02—Hollow fibre modules
    • B01D63/021—Manufacturing thereof
    • B01D63/022—Encapsulating hollow fibres
    • B01D63/023—Encapsulating materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • C08G18/3278—Hydroxyamines containing at least three hydroxy groups
    • C08G18/3284—Hydroxyamines containing at least three hydroxy groups containing four hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds

Definitions

  • the present invention relates to a polyurethane resin-forming composition and a sealing material using the composition.
  • hollow fiber membrane modules using hollow fibers as separation membranes are widely used in industrial fields such as water treatment membranes and medical fields such as blood treatment. Especially for applications such as water purifiers, artificial kidneys, and artificial lungs, the demand is extremely increasing.
  • a hollow fiber membrane module it is widely used a polyurethane resin excellent in flexibility, adhesiveness and chemical resistance at normal temperature as a sealing material for bonding and fixing the end portion where the hollow fiber membranes are converged.
  • a polyurethane resin excellent in flexibility, adhesiveness and chemical resistance at normal temperature as a sealing material for bonding and fixing the end portion where the hollow fiber membranes are converged.
  • hollow fibers used in hollow fiber membrane modules are made of glycerin-containing hollow fibers in which a retaining agent (glycerin) is used to maintain pores, and synthetic polymers as raw materials.
  • a retaining agent glycerin
  • non-containing glycerin-free hollow fibers There are non-containing glycerin-free hollow fibers.
  • MDI polyurethane resin-forming composition containing diphenylmethane diisocyanate
  • a low-molecular reaction product of MDI and glycerin is generated. It is known that the reaction product dissolves into the blood and adversely affects the human body.
  • TDI toluene diisocyanate
  • HDI hexamethylene diisocyanate
  • the potting material system is different between the glycerin-containing hollow fiber and the glycerin-free hollow fiber, in the membrane module using the glycerin-containing hollow fiber, in addition to the method of introducing the TDI or the HDI
  • Patent Document 2 As a method for obtaining a sealing material, for example, in Japanese Patent Application Laid-Open No. 7-213871 (Patent Document 2), an isocyanate group-terminated prepolymer obtained from a reaction product of polymethylene polyphenyl polyisocyanate and MDI and castor oil is used as an isocyanate component.
  • a polyurethane resin obtained by curing a polymer with a polyol has been proposed.
  • the polyurethane resin described in Patent Document 2 although MDI is reacted with castor oil and polymethylene polyphenyl polyisocyanate is added to lower the viscosity, the viscosity of the main agent is high. And the curing viscosity of the curing agent is high.
  • the filling rate of hollow fibers has been further increased, and from the viewpoint of permeability to details, the polyurethane resin described in Patent Document 2 is concerned with poor filling during molding.
  • the present invention has been made in view of the above problems, and a polyurethane resin-forming composition capable of achieving both low elution of a reaction product of MDI and glycerin and reduction in mixed viscosity and the composition. It is in providing the sealing material using this.
  • a polyurethane resin-forming composition comprising a main agent (A) containing an isocyanate component and a curing agent (B) containing a polyol component.
  • a polyurethane resin-forming composition for a hollow fiber membrane module sealing material comprising a main component (A) containing an isocyanate component and a curing agent (B) containing a polyol component
  • an isocyanate component constituting the main agent (A) Obtained by reacting polyisocyanate (hereinafter referred to as pomeric MDI) (a1), which is a mixture of diphenylmethane diisocyanate and polymethylene polyphenyl polyisocyanate, with an aliphatic alcohol (a2) having 10 to 15 carbon atoms, and isocyanate
  • pomeric MDI polyisocyanate
  • a1 which is a mixture of diphenylmethane diisocyanate and polymethylene polyphenyl polyisocyanate
  • an aliphatic alcohol (a2) having 10 to 15 carbon atoms
  • isocyanate An isocyanate group-terminated prepolymer having a group (NCO) content of 15.0 to 21.5% by mass
  • the mass ratio of the diphenylmethane diisocyanate to the polymethylene polyphenyl polyisocyanate is 20/80 to 80/20.
  • a polyurethane resin-forming composition capable of achieving both low elution of a reaction product of MDI and glycerin and reduction in mixed viscosity, and a sealing material using the composition.
  • a polyurethane resin-forming composition having an elution amount of a reaction product of MDI and glycerin (low molecular eluate value) and a low viscosity and good filling property when a membrane module is produced is obtained. I can do it. Further, by using the polyurethane resin-forming composition of the present invention, it becomes possible to provide a sealing material useful as a sealing material for a hollow fiber membrane module or the like without considering the presence or absence of glycerin contained in the hollow fiber.
  • the polyurethane resin-forming composition of the present invention comprises a main agent (A) containing an isocyanate component and a curing agent (B) containing a polyol component.
  • the main agent (A) according to the present invention is obtained by reacting, as an isocyanate component, polymeric MDI (a1) and an aliphatic alcohol (a2) having 10 to 15 carbon atoms, and has an isocyanate group (NCO) content. Contains an isocyanate group-terminated prepolymer of 15.0 to 21.5% by mass.
  • the polymeric MDI (a1) is a mixture of diphenylmethane diisocyanate (MDI) (a1-1) and polymethylene polyphenyl polyisocyanate (a1-2).
  • MDI diphenylmethane diisocyanate
  • a1-2 polymethylene polyphenyl polyisocyanate
  • the MDI (a1-1) has two isocyanate groups and two benzene rings, and is called a so-called dinuclear body.
  • the polymethylene polyphenylene polyisocyanate (a1-2) has three or more isocyanate groups and benzene rings, and is called a so-called polynuclear body.
  • the mass ratio of the MDI (a1-1) to the polymethylene polyphenyl polyisocyanate (a1-2) is 20/80 to 80 / 20 is preferable, and 30/70 to 45/55 is more preferable.
  • the ratio (a1-1) is less than the lower limit, filling failure tends to occur due to an increase in viscosity.
  • the said upper limit is exceeded, the low temperature storage stability of the main ingredient (A) obtained will fall, and it exists in the tendency for a low molecular eluate value to increase.
  • the composition ratio of isomers in the MDI (a1-1) is such that the total content of 2,2′-MDI and 2,4′-MDI is 20 masses based on the total mass of the MDI (a1-1). % Or less, more preferably 10% by mass or less.
  • the total content of 2,2′-MDI and 2,4′-MDI exceeds the upper limit, the reactivity of the resulting polyurethane resin-forming composition is lowered, and a cured resin and one type of seal are included. There is concern about a decrease in the hardness of the material.
  • the aliphatic alcohol (a2) needs to have 10 to 15 carbon atoms (decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol), and further has a carbon number. Is preferably 12-14. When the number of carbon atoms is less than the lower limit, the viscosity of the isocyanate group-terminated prepolymer is increased, so that problems such as poor packing properties at the time of molding the membrane module and peeling at the time of cutting in the resulting cured resin occur.
  • the isocyanate group-terminated prepolymer according to the present invention is obtained by reacting the polymeric MDI (a1) and the aliphatic alcohol (a2).
  • reaction for obtaining the said isocyanate group terminal prepolymer the urethanation reaction normally performed can be employ
  • the isocyanate group content of the isocyanate group-terminated prepolymer according to the present invention is 15.0 to 21.5% by mass, preferably 16.0 to 20.0% by mass, and more preferably 16.0 to 18.0%. % By mass.
  • an isocyanate compound other than the polymeric MDI (a1) and an isocyanate compound other than the polymeric MDI (a1) may be used as long as the effects of the present invention are not impaired.
  • an aliphatic alcohol (a2) may be further included as an isocyanate component.
  • isocyanate compounds other than the polymeric MDI (a1) include TDI, xylene diisocyanate, nitrodiphenyl diisocyanate, diphenylpropane diisocyanate, dimethyldiphenylmethane diisocyanate, phenylene diisocyanate, naphthylene diisocyanate, dimethoxydiphenyl diisocyanate, tetramethylene diisocyanate, HDI, and methyl.
  • Isocyanates such as pentane diisocyanate, lysine diisocyanate, isophorone diisocyanate, hydrogenated TDI, hydrogenated xylene diisocyanate, hydrogenated MDI, tetramethylxylene diisocyanate; polymeric, urethane-modified, urea-modified, allophanate-modified, biuret of these isocyanates Degeneration , Carbodiimide-modified products, uretonimine modified product, uretdione modified product, an isocyanurate modified product, and the like, may be even one of these or two or more kinds.
  • the curing agent (B) contains, as a polyol component, at least one (b1) selected from the group consisting of castor oil and castor oil-based modified polyol, and a hydroxyl group-containing amine compound (b2). .
  • the castor oil and castor oil-based modified polyol (b1) is obtained by the reaction of castor oil, castor oil fatty acid and polyol (at least one selected from the group consisting of low molecular polyols and polyether polyols).
  • the polyester include, for example, castor oil fatty acid diglyceride and monoglyceride; castor oil fatty acid and trimethylol alkane mono, di, triester; castor oil fatty acid and polypropylene glycol Mono, di, triester and the like can be mentioned.
  • the main component of the castor oil is triglyceride of ricinoleic acid, and in the present invention, the castor oil includes hydrogenated castor oil.
  • the main component of the castor oil fatty acid is ricinoleic acid.
  • the castor oil fatty acid includes hydrogenated castor oil fatty acid.
  • trimethylol alkane examples include trimethylol methane, trimethylol ethane, trimethylol propane, trimethylol butane, trimethylol pentane, trimethylol hexane, trimethylol heptane, trimethylol octane, trimethylol nonane, trimethylol decane. Is mentioned.
  • the number average molecular weight of the castor oil and castor oil-based modified polyol (b1) according to the present invention is preferably 400 to 3000, and more preferably 500 to 2500.
  • the sealing material is required.
  • the cured resin having good physical properties (particularly mechanical properties) can be formed.
  • the average hydroxyl value of castor oil and castor oil-modified polyol (b1) according to the present invention is preferably 20 to 300 mgKOH / g, more preferably 40 to 250 mgKOH / g.
  • the sealing material is required.
  • the cured resin having good physical properties (particularly mechanical properties) can be formed, and the productivity of the sealing material, and hence the productivity of the hollow fiber membrane module (filter device) can be improved.
  • hydroxyl group-containing amine compound (b2) examples include a low molecular polyamine and a low molecular amino alcohol (for example, ethylenediamine which is an oxyalkylated derivative of an amino compound (N, N, N ′, N′-tetrakis [ 2-hydroxypropyl] ethylenediamine, N, N, N ′, N′-tetrakis [2-hydroxyethyl] ethylenediamine, etc.) propylene oxide or ethylene oxide adduct; mono-, di-, triethanolamine; N-methyl-N, And amine compounds such as N′-diethanolamine).
  • ethylenediamine which is an oxyalkylated derivative of an amino compound (N, N, N ′, N′-tetrakis [ 2-hydroxypropyl] ethylenediamine, N, N, N ′, N′-tetrakis [2-hydroxyethyl] ethylenediamine, etc.
  • propylene oxide or ethylene oxide adduct such as ethylenediamine is preferable, and N, N, N ′, N′-tetrakis [2-hydroxypropyl] ethylenediamine is most preferable.
  • N, N, N ′, N′-tetrakis [2-hydroxypropyl] ethylenediamine the processability at the time of molding is further improved, and the low molecular eluate value tends to be further decreased.
  • the cured resin formed by the polyurethane resin-forming composition of the present invention and the sealing material which is one type thereof are particularly excellent in moldability, adhesiveness and heat resistance.
  • a mass ratio ((1) selected from the group consisting of castor oil and castor oil-modified polyol (b1) and the hydroxyl group-containing amine compound (b2) (( The mass of b1) / the mass of (b2)) is preferably 85/15 to 75/25, more preferably 83/17 to 77/23.
  • the ratio of the hydroxyl group-containing amine compound (b2) is less than the lower limit, the reactivity of the polyurethane resin-forming composition is deteriorated, and the resulting cured resin and the hardness of the sealing material that is one type thereof are low.
  • active hydrogen group-containing compound in the curing agent (B), at least one selected from the group consisting of castor oil and castor oil-based modified polyol (b1) and active hydrogen other than the hydroxyl group-containing amine compound (b2)
  • a group-containing compound hereinafter referred to as “active hydrogen group-containing compound (b3)”) may further be contained.
  • Examples of the active hydrogen group-containing compound (b3) include polyols such as low-molecular polyols, polyether-based polyols, polyester-based polyols, polylactone-based polyols, and polyolefin-based polyols. These may be used alone or in combination of two or more. Can be used in combination.
  • low molecular polyol examples include ethylene glycol, diethylene glycol, propylene glycol, 1,2- / 1,3- / 1,4-butanediol, 1,5-pentanediol, and 3-methyl-1,5-pentane.
  • Divalent polyols such as diol, 1,6-hexane glycol, 1,8-octanediol, 1,10-decanediol, neopentyl glycol, hydrogenated bisphenol A; glycerin, trimethylolpropane, hexane
  • examples thereof include tri to octavalent polyols such as triol, pentaerythritol, sorbitol, and shoelace.
  • the molecular weight of such a low molecular polyol is usually 50 to 200.
  • the polyether-based polyol is a polymerization obtained by using the above low-molecular-weight polyol as an initiator and adding alkylene oxide (for example, alkylene oxide having 2 to 8 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide) to this.
  • alkylene oxide for example, alkylene oxide having 2 to 8 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide
  • Specific examples include polypropylene glycol, polyethylene glycol, PTMG, and chipped ether that is a copolymer of ethylene oxide and propylene oxide.
  • the molecular weight of such a polyether polyol is usually 200 to 7000, preferably 500 to 5000.
  • a polyether-based polyol having a molecular weight within the above range By using a polyether-based polyol having a molecular weight within the above range, a polyurethane resin-forming composition particularly excellent in molding processability when forming a sealing material, particularly when the sealing material is used for producing a hollow fiber membrane module Things are obtained.
  • polyester polyol examples include polycarboxylic acids (saturated or unsaturated aliphatic polycarboxylic acids such as azelaic acid, dodecanoic acid, maleic acid, fumaric acid, itaconic acid, ricinoleic acid and dimerized linoleic acid; phthalic acid, isophthalic acid
  • polycarboxylic acids saturated or unsaturated aliphatic polycarboxylic acids such as azelaic acid, dodecanoic acid, maleic acid, fumaric acid, itaconic acid, ricinoleic acid and dimerized linoleic acid
  • phthalic acid isophthalic acid
  • the molecular weight of such a polyester-based polyol is usually 200 to 5000, preferably 500 to 3000.
  • a polyurethane resin-forming composition that is particularly excellent in molding processability when forming a sealing material, particularly when the sealing material is used for producing a hollow fiber membrane module Is obtained.
  • polylactone-based polyol examples include polymerization initiators such as glycols and triols, ⁇ -caprolactone, ⁇ -methyl- ⁇ -caprolactone, ⁇ -methyl- ⁇ -caprolactone, and ⁇ -methyl- ⁇ -valerolactone. And polyols obtained by addition polymerization in the presence of a catalyst such as an organometallic compound, a metal chelate compound, or a fatty acid metal acyl compound.
  • a catalyst such as an organometallic compound, a metal chelate compound, or a fatty acid metal acyl compound.
  • the molecular weight of such a polylactone-based polyol is usually 200 to 5000, preferably 500 to 3000.
  • a polyurethane resin-forming composition that is particularly excellent in molding processability when forming a sealing material, particularly when the sealing material is used for producing a hollow fiber membrane module Is obtained.
  • polystyrene-based polyol examples include polybutadiene and a polybutadiene-based polyol in which a hydroxyl group is introduced at the terminal of a copolymer of butadiene and styrene or acrylonitrile.
  • polyether ester polyol obtained by addition-reacting an alkylene oxide for example, ethylene oxide, propylene oxide, etc.
  • an alkylene oxide for example, ethylene oxide, propylene oxide, etc.
  • a polyester having at least one of a carboxyl group and an OH group at the terminal is also the active hydrogen group-containing compound. It can be used as (b3).
  • the mass of (b3)) is preferably 50:50 to 100: 0, particularly preferably 100: 0.
  • the ratio is: ⁇ (mass of (b1)) + (mass of (b3)) ⁇ / (Mass of (b2)) is preferably 85/15 to 75/25, and from the viewpoint of excellent curability and fillability of the polyurethane resin-forming composition, 83/17 More preferably, it is -77/23.
  • the mixing ratio of the main agent (A) and the curing agent (B) is an isocyanate group in the isocyanate component constituting the main agent (A), and the curing agent (B Polyol component (at least one selected from the group consisting of castor oil and castor oil-based modified polyol (b1), a hydroxyl group-containing amine compound (b2) and an optional active hydrogen group-containing compound (b3)) It is preferable that the molar ratio (number of moles of isocyanate group / number of moles of active hydrogen group) with the active hydrogen group in the ratio is 0.8 to 1.6, more preferably 0.9 to 1.
  • the polyurethane resin-forming composition obtained in such a mixing ratio it is possible to form a cured resin excellent in durability and a very small amount of low-molecular eluate in water and a sealing material that is one type thereof. it can.
  • the polyurethane resin-forming composition of the present invention may further contain a known urethanization catalyst.
  • a known urethanization catalyst include metal compound catalysts such as organotin compounds; triethylenediamine (TEDA), tetramethylhexamethylenediamine (TMHMDA), pentamethyldiethylenetriamine (PMDETA), dimethylcyclohexylamine (DMCHA), bisdimethylaminoethyl.
  • TMHMDA triethylenediamine
  • TMHMDA tetramethylhexamethylenediamine
  • PMDETA pentamethyldiethylenetriamine
  • DMCHA dimethylcyclohexylamine
  • BDMAEA tertiary amine catalysts
  • BDMAEA ether
  • the mixing viscosity of the main agent (A) and the curing agent (B) is sufficiently low, and according to the polyurethane resin-forming composition of the present invention, MDI and A cured resin having a sufficiently small elution amount of the reaction product with glycerin (low molecular eluate value) and a sealing material that is one type thereof can be obtained.
  • the sealing material of the present invention comprises a cured resin obtained by curing the polyurethane resin-forming composition of the present invention.
  • the polyurethane resin-forming composition of the present invention comprising the main agent (A) and the curing agent (B) is prepared at room temperature, and is 0 ° C to 100 ° C, preferably 30 ° C to 80 ° C. More preferably, it is preferably formed by reacting and curing the isocyanate component constituting the main agent (A) and the polyol component constituting the curing agent (B) under a temperature condition of 30 ° C. to 60 ° C. Can do.
  • each of the main agent (A) and the curing agent (B) is heated to 30 to 60 ° C. before mixing as necessary. You may use it warm.
  • the hollow fiber membrane module of the present invention includes the sealing material of the present invention.
  • the gaps between the hollow fiber membranes at the ends of a plurality of hollow fiber membrane bundles are sealed with the polyurethane resin-forming composition of the present invention, and the composition is cured to thereby form the present invention.
  • a specific structure of the hollow fiber membrane module (hollow fiber membrane filtration device) of the present invention a known structure can be adopted as appropriate, for example, a structure described in JP-A-11-5023. Yes, but not limited to this.
  • main agent (A-1) the isocyanate group-terminated prepolymer had an isocyanate group (NCO) content of 17.5% by mass and a viscosity at 25 ° C. of 2860 mPa ⁇ s.
  • Example 1 [Low molecular eluate value measurement sample] First, the mass ratio (mass of (A-1) / mass of (B-1)) of the main agent (A-1) (liquid temperature 50 ° C.) and the curing agent (B-1) (liquid temperature 50 ° C.) The mixture was mixed so that the total mass became 80 g and manually stirred for 15 seconds using a spatula. Next, 40 g of glycerin was added to the mixed solution and further stirred for 15 seconds to obtain a polyurethane resin-forming composition.
  • This polyurethane resin-forming composition (100 g) was cast into a cartridge case (made of polycarbonate with an inner diameter of 48 mm) in a centrifugal molding machine and subjected to centrifugal molding to obtain a cured resin (low molecular eluate value measurement sample).
  • Centrifugal molding conditions were as follows: the primary curing condition was 1500 rpm at a centrifugal molding machine, the temperature was 50 ° C., and the time was 10 minutes, and the secondary curing condition was left in the thermostatic layer at a temperature of 45 ° C. and a time of 2 days.
  • Examples 2 to 4, Comparative Examples 1 to 4 instead of the main agent (A-1), the main agents (A-2) to (A-8) obtained in Production Examples 2 to 8 shown in Tables 1 and 2, respectively, were used, and the mass ratio of the main agent to the curing agent was changed.
  • a cured resin (low molecular eluate value measurement sample and hardness measurement sample) was obtained in the same manner as in Example 1 except that the mass ratios shown in Tables 1 and 2 were used.
  • the obtained extract was decanted and 10 ml was placed in a 50 ml volumetric flask, and the liquid adjusted to 50 ml by adding purified water was used as a test solution, and UV absorbance measurement (Shimadzu Corporation UV-1500) was performed.
  • the maximum value of absorbance at 240-245 nm / 10 was defined as the low molecular eluate value.
  • the hardness of the cured resin obtained in each example and comparative example was measured by the following method.
  • the JIS-D hardness after 10 seconds from the measurement moment and the measurement moment under the temperature condition of 25 ° C. is a method based on the method described in JIS-K7312. It was measured.
  • the content (peak area%) of MDI in the main agent obtained in each production example is gel permeation chromatography (GPC) (measuring instrument: “HLC-8120” (manufactured by Tosoh Corporation).
  • GPC gel permeation chromatography
  • HLC-8120 manufactured by Tosoh Corporation
  • THF tetrahydrofuran
  • detector differential refraction
  • sample THF 0.5% solution
  • the results obtained by conducting the mixed viscosity measurement, the low-molecular eluate extraction test and the hardness measurement test in each Example and Comparative Example are the results of the composition of each polyurethane resin-forming composition (combination of main agent and curing agent and mass ratio).
  • Tables 1 and 2 together with the NCO content of the isocyanate group-terminated prepolymer in the main agent are shown.
  • Table 3 shows the viscosity of the main agent, the MDI content, and the NCO content in the isocyanate group-terminated prepolymer (simply referred to as NCO content in Table 3) in each production example.
  • the polyurethane resin-forming composition which can make compatible the low elution of the reaction material of MDI and glycerol, and the reduction of a mixing viscosity, and the sealing material using the said composition.
  • the cured resin obtained by curing the polyurethane resin-forming composition of the present invention has many excellent performances, particularly excellent low elution physical properties.
  • the sealing material of the present invention which is one of the cured resins, is used as a sealing material (binding material) for a hollow fiber membrane module (hollow fiber membrane filtration device) constituting a medical or industrial separation device. And can be suitably used as a sealing material for a hollow fiber membrane module.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne une composition formant une résine de polyuréthanne pour un produit d'étanchéité pour un module de membrane en fibre creuse, comprenant un agent principal (A) contenant un composant d'isocyanate et un agent de durcissement (B) contenant un composant de polyol, où comme composant d'isocyanate constituant l'agent principal (A), un prépolymère terminé par un groupe isocyanate, qui est obtenu par réaction de MDI polymère (a1) qui est un mélange de diisocyanate de diphénylméthane et de polyisocyanate de polyméthylène polyphényle avec un alcool aliphatique (a2) ayant 10 à 15 atomes de carbone et a une teneur en groupe isocyanate de 15,0 à 21,5% en masse est contenu, et comme composant de polyol constituant l'agent de durcissement (B), au moins un membre (b1) sélectionné parmi un groupe constitué d'huile de ricin et de polyols modifiés à base d'huile de ricin et un composé à base d'amine contenant un groupe hydroxy (b2) sont contenus.
PCT/JP2011/064776 2010-06-29 2011-06-28 Composition formant une résine de polyuréthanne et produit d'étanchéité WO2012002370A1 (fr)

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* Cited by examiner, † Cited by third party
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CN105396470A (zh) * 2015-12-10 2016-03-16 广州中国科学院先进技术研究所 中空纤维复合纳滤膜及其制备方法
JP2017006874A (ja) * 2015-06-24 2017-01-12 三洋化成工業株式会社 血液処理器に用いられる膜モジュールのシール材用ポリウレタン樹脂形成性組成物
JP2018119084A (ja) * 2017-01-26 2018-08-02 東ソー株式会社 アロファネート基含有ポリイソシアネート組成物
JP2019006856A (ja) * 2017-06-21 2019-01-17 東ソー株式会社 膜シール材用ポリウレタン樹脂形成性組成物、これを用いたシール材、及び中空糸膜モジュール
WO2020021203A1 (fr) * 2018-07-27 2020-01-30 Bostik Sa Composition a base de polyurethane pour la preparation de resine

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JPS4862745A (fr) * 1971-12-08 1973-09-01
JPH07149857A (ja) * 1993-09-02 1995-06-13 Miles Inc 液体ジフェニルメタンジイソシアネート並びにその製造および使用方法
JP2007224078A (ja) * 2006-02-21 2007-09-06 Nippon Polyurethane Ind Co Ltd 中空糸膜モジュールに用いられるシール材用ポリウレタン樹脂形成性組成物、及び該組成物を用いた中空糸膜モジュール用シール材
WO2009013902A1 (fr) * 2007-07-24 2009-01-29 Nippon Polyurethane Industry Co., Ltd. Composition formant une résine de polyuréthane et un matériau d'étanchéité

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4862745A (fr) * 1971-12-08 1973-09-01
JPH07149857A (ja) * 1993-09-02 1995-06-13 Miles Inc 液体ジフェニルメタンジイソシアネート並びにその製造および使用方法
JP2007224078A (ja) * 2006-02-21 2007-09-06 Nippon Polyurethane Ind Co Ltd 中空糸膜モジュールに用いられるシール材用ポリウレタン樹脂形成性組成物、及び該組成物を用いた中空糸膜モジュール用シール材
WO2009013902A1 (fr) * 2007-07-24 2009-01-29 Nippon Polyurethane Industry Co., Ltd. Composition formant une résine de polyuréthane et un matériau d'étanchéité

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017006874A (ja) * 2015-06-24 2017-01-12 三洋化成工業株式会社 血液処理器に用いられる膜モジュールのシール材用ポリウレタン樹脂形成性組成物
CN105396470A (zh) * 2015-12-10 2016-03-16 广州中国科学院先进技术研究所 中空纤维复合纳滤膜及其制备方法
CN105396470B (zh) * 2015-12-10 2018-04-06 广州中国科学院先进技术研究所 中空纤维复合纳滤膜及其制备方法
JP2018119084A (ja) * 2017-01-26 2018-08-02 東ソー株式会社 アロファネート基含有ポリイソシアネート組成物
JP7069541B2 (ja) 2017-01-26 2022-05-18 東ソー株式会社 アロファネート基含有ポリイソシアネート組成物
JP2019006856A (ja) * 2017-06-21 2019-01-17 東ソー株式会社 膜シール材用ポリウレタン樹脂形成性組成物、これを用いたシール材、及び中空糸膜モジュール
JP7135279B2 (ja) 2017-06-21 2022-09-13 東ソー株式会社 膜シール材用ポリウレタン樹脂形成性組成物、これを用いたシール材、及び中空糸膜モジュール
WO2020021203A1 (fr) * 2018-07-27 2020-01-30 Bostik Sa Composition a base de polyurethane pour la preparation de resine
FR3084368A1 (fr) * 2018-07-27 2020-01-31 Bostik Sa Composition a base de polyurethane pour la preparation de resine

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