WO2013146263A1 - Composition générant une résine de polyuréthane utilisable à des fins de scellement d'un module membranaire - Google Patents

Composition générant une résine de polyuréthane utilisable à des fins de scellement d'un module membranaire Download PDF

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Publication number
WO2013146263A1
WO2013146263A1 PCT/JP2013/056989 JP2013056989W WO2013146263A1 WO 2013146263 A1 WO2013146263 A1 WO 2013146263A1 JP 2013056989 W JP2013056989 W JP 2013056989W WO 2013146263 A1 WO2013146263 A1 WO 2013146263A1
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Prior art keywords
polyol
group
weight
membrane module
compound
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PCT/JP2013/056989
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English (en)
Japanese (ja)
Inventor
島田　哲也
ゆう子 住友
政登 今井
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三洋化成工業株式会社
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Priority to CN201380009230.8A priority Critical patent/CN104114261B/zh
Priority to JP2014507645A priority patent/JP5802329B2/ja
Publication of WO2013146263A1 publication Critical patent/WO2013146263A1/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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4866—Polyethers having a low unsaturation value
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4891—Polyethers modified with higher fatty oils or their acids or by resin acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
    • C09K3/1021—Polyurethanes or derivatives thereof
    • 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
    • C08G2190/00—Compositions for sealing or packing joints

Definitions

  • the present invention relates to a polyurethane resin-forming composition for a sealing material of a membrane module particularly suitable for a sealing material of a hollow fiber type blood treatment device or water purifier.
  • N , N, N ′, N′-tetrakis (2-hydroxypropyl) -ethylenediamine is known (for example, see Patent Document 1).
  • a polyurethane resin-forming composition for a sealing material of a membrane module that is fast-curing and has low viscosity and excellent castability
  • a polyol component (A) comprising a polyoxyalkylene polyol (a) and an organic polyisocyanate component
  • the polyurethane resin-forming composition comprising (B) comprises (a) a polyoxyalkylene polyol (a) having a hydroxypropyl end and a primary hydroxyl group content of at least 40%.
  • a polyurethane resin-forming composition for a sealing material for a treatment device or a water purifier is known (for example, see Patent Document 2).
  • a polyurethane resin for a sealing material of a membrane module using a conventional castor oil-based polyol or polyoxypropylene polyol and a mixture of N, N, N ′, N′-tetrakis (2-hydroxypropyl) -ethylenediamine as a polyol component.
  • the viscosity of the mixed liquid before casting becomes high, and there is a problem that casting work is difficult.
  • the curability and the resin physical properties may be insufficient although the viscosity is low.
  • odor is generated in the liquid treated with the membrane module or the taste becomes specific when used in a water purifier.
  • An object of the present invention is a polyurethane resin-forming composition for a sealing material of a membrane module, which has a low viscosity and excellent curability, has little odor of the processing solution by the membrane module, and hardly generates a specific taste in the processing solution. Is to provide.
  • the present invention relates to a polyurethane resin for a sealing material of a membrane module comprising a polyol component (A) containing a polyoxyalkylene polyol (a) and / or its ethylene oxide adduct (b) and an organic polyisocyanate component (B).
  • the contents of (a) and (b) of the by-product low-boiling compound (t) having a boiling point at atmospheric pressure of 150 ° C. or less at the normal pressure are (a) and (b), respectively.
  • a polyurethane resin-forming composition for a sealing material of a membrane module characterized in that it is 0.020% by weight or less based on the weight of the membrane module; a membrane module comprising the composition Sealant le; membrane module formed by sealing with the sealing member; and a hollow fiber type blood treating device and water purifier comprising using the membrane module.
  • the polyurethane resin-forming composition for a sealing material of a membrane module of the present invention has a small amount of terminal unsaturated group-containing monool produced by side reactions (transfer, oxidation, etc.) in producing the polyoxyalkylene polyol (a) to be used. Therefore, the curing reaction is hardly inhibited, and since there are few by-product low-boiling compounds having a boiling point of 150 ° C. or less at normal pressure (pressure 0.1 MPa) generated by the side reaction, the following effects are obtained.
  • the cured polyurethane resin has high physical properties (breaking strength, hardness after curing at 25 ° C. for 4 days, etc.) and excellent durability.
  • a polyurethane resin-forming composition for a sealing material of a membrane module of the present invention comprises a polyol component (A) containing a polyoxyalkylene polyol (a) and / or an ethylene oxide adduct (b) thereof and an organic polyisocyanate component (B).
  • a polyurethane resin-forming composition for a sealing material of a membrane module comprising: (a) a molecular end of which is a hydroxypropyl group and a primary hydroxyl group content thereof is at least 40%, (a) and ( The contents of (a) and (b) of the by-product low-boiling compound (t) having a total unsaturation of b) of 0.010 meq / g or less and a boiling point of 150 ° C. or less at normal pressure are (a ) And (b) based on the weight of 0.020% by weight or less of the polyurethane resin-forming composition.
  • Examples of the polyoxyalkylene polyol (a) include compounds represented by the general formula (1).
  • X in the general formula (1) is an m-valent residue obtained by removing active hydrogen atoms from a compound having m active hydrogen atoms, and m is an integer of 2 to 20.
  • m is an integer of 2 to 20.
  • the compound having m active hydrogen atoms constituting the residue X includes a hydroxyl group-containing compound, an amino group-containing compound, a carboxyl group-containing compound, and a thiol, a hydroxyl group, a primary or secondary amino group, a carboxyl group, and a mercapto. And compounds having at least one group selected from the group.
  • hydroxyl group-containing compound examples include low molecular weight polyhydric alcohols having a hydroxyl group equivalent of 160 or less [aliphatic polyhydric alcohols [aliphatic dihydric alcohols having 2 to 20 carbon atoms ⁇ alkylene glycols such as ethylene glycol, propylene glycol, 1, 3 -Butylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methylpentanediol, neopentylglycol, 1,9-nonanediol, etc .; 3 to 8 or more valences having 3 to 8 carbon atoms Polyhydric alcohols ⁇ glycerin, trimethylolpropane, pentaerythritol, sorbitol, xylitol, mannitol, etc. ⁇ ; intermolecular or intramolecular dehydrates such as dipentaerythritol, polyglycerin (degree of polymer
  • the number average molecular weight in the present invention is measured by gel permeation chromatography using tetrahydrofuran as a solvent and polyoxypropylene glycol as a standard substance.
  • the sample concentration may be 0.25% by weight
  • the column stationary phase may be TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 (both manufactured by Tosoh Corporation), and the column temperature may be 40 ° C.
  • amino group-containing compounds include primary monoamines [mono (cyclo) alkylamines having 1 to 20 carbon atoms (methylamine, ethylamine, butylamine, octylamine, dodecylamine, cyclohexylamine, etc.), aromatics having 6 to 12 carbon atoms.
  • Aliphatic and araliphatic monoamines (aniline, toluidine, benzylamine, etc.)]; polyamines having two or more active hydrogens [aliphatic diamines having 2 to 12 or more carbon atoms ⁇ alkylene diamines such as ethylene diamine, propylene diamine, Hexamethylene diamine, mono- or di-alkyl (carbon number 1 to 4) alkylene diamine (dimethylpropylene diamine, etc.) ⁇ , alicyclic diamine having 6 to 15 carbon atoms (1,4-diaminocyclohexane, isophorone diamine) And 4,4'-diaminosic Hexylmethane, etc.), aromatic diamines having 6 to 15 carbon atoms ⁇ m- or p-phenylenediamine, tolylenediamine, diethyltoluenediamine, 4,4'-diaminophenylmethane and 2,2-bis (4,4 ' -Diaminoph
  • carboxyl group-containing compound examples include aliphatic polycarboxylic acids having 2 to 36 carbon atoms (such as succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, and dimerized linoleic acid), and those having 8 to 15 carbon atoms.
  • Aromatic polycarboxylic acid phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.
  • unsaturated carboxylic acid polymer [(meth) acrylic acid (co) polymerization with a number average molecular weight of 2,000 or less And the like, and mixtures of two or more thereof.
  • thiols include divalent to octavalent polythiols having 2 to 6 or more carbon atoms (ethanedithiol, propanedithiol, 1,3- or 1,4-butanedithiol, 1,6-hexanedithiol, 3-methyl- 1,5-pentanedithiol and the like.
  • a hydroxyl group-containing compound and an amino group-containing compound are preferable, and an aliphatic polyhydric alcohol having a hydroxyl group equivalent of 160 or less and a castor oil-based polyol (d) described below, particularly propylene glycol, Glycerin, pentaerythritol, dipentaerythritol, polyglycerol (degree of polymerization 2 to 10) and castor oil.
  • d castor oil-based polyol
  • a in the general formula (1) is a phenyl group or an alkylene group having 2 to 12 carbon atoms which may be substituted with a halogen atom, a straight chain or branched alkylene group having 2 to 12 carbon atoms, 10 cycloalkylene groups, and those substituted with these phenyl groups, halophenyl groups, or halogen atoms (Cl, Br, etc.).
  • A examples include an ethylene group, 1,2- or 1,3-propylene group, 1,2-, 2,3-, 1,3- or 1,4-butylene group, having 5 to 12 carbon atoms.
  • Examples include 1,2-alkylene groups (such as 1,2-dodecylene group), 1,2-cyclohexylene group, chloropropylene group, bromopropylene group, phenylethylene group and chlorophenylethylene group.
  • AO alkylene oxide
  • EO ethylene oxide
  • PO 1,2-propylene oxide
  • BO 1,3-propylene oxide
  • BO butylene oxide
  • ⁇ -olefin oxide having 5 to 12 carbon atoms epihalohydrin (epichlorohydrin, epibromohydrin, etc.)
  • styrene oxide 1,2 -Cyclohexene oxide and a combination of two or more of these may be mentioned, and the bonding mode when p (AO) is composed of two or more oxyalkylene groups may be either block or random.
  • PO and 1,2-BO are preferred.
  • Z in the general formula (1) is a propylene group, p is 0 or an integer from 1 to 199, q is an integer from 1 to 200, and satisfies p + q ⁇ 200.
  • the polyoxyalkylene polyol (a) has a hydroxypropyl group at the terminal. Confirmation of having a hydroxypropyl group terminal can be carried out, for example, by 1 H-NMR method.
  • the hydroxypropyl group includes a primary hydroxyl group (hydroxyl group bonded to primary carbon) represented by the following chemical formula (2) and a secondary hydroxyl group (bonded to secondary carbon) represented by the chemical formula (2 ′). Hydroxyl group) -containing groups, but the primary hydroxyl group content (hereinafter referred to as the primary ratio), which is the ratio of the number of primary hydroxyl group-containing groups to the total number of primary hydroxyl group-containing groups and secondary hydroxyl group-containing groups. Is usually 40% or more, preferably 70% or more. If the primary rate is less than 40%, sufficient rapid curability cannot be obtained.
  • the primary rate can be determined by pretreatment (esterification) of the sample in advance and then measuring by 1 H-NMR method.
  • sample preparation method About 30 mg of a measurement sample is weighed into an NMR sample tube having a diameter of 5 mm, and about 0.5 ml of deuterated solvent is added and dissolved. Thereafter, about 0.1 ml of trifluoroacetic anhydride is added to obtain a sample for analysis.
  • the deuterated solvent for example, a solvent capable of dissolving the sample is appropriately selected from deuterated chloroform, deuterated toluene, deuterated dimethyl sulfoxide, deuterated dimethylformamide, and the like.
  • (A) can be produced, for example, by the method described in JP-A No. 2000-344881.
  • TPB tris (pentafluorophenyl) borane catalyst
  • TPB tris (pentafluorophenyl) borane catalyst
  • X, A and m in the general formula (3) are the same as those in the general formula (1), and p is 0 or an integer of 1 to 199.
  • (a0) include those exemplified as the compound having m active hydrogen atoms constituting the residue of the general formula (1) when p is 0.
  • (a0) when p is 1 or more is a polyol obtained by (co) adding AO to a compound constituting the residue X using a conventionally known catalyst (such as an alkali metal hydroxide);
  • a conventionally known catalyst such as an alkali metal hydroxide
  • Preferable examples include propylene glycol PO adduct, glycerin PO adduct, polyglycerin PO adduct, propylene glycol 1,2-BO adduct, glycerin 1,2-BO adduct, polyglycerin 1,
  • Examples include 2-BO adducts, PO / 1,2-BO coadducts of glycerin (block or random), and the like.
  • the amount of TPB used in producing (a) by subjecting PO to (a0) to ring-opening addition polymerization is not particularly limited, but is usually 0.00005 to 10% by weight, preferably 0, based on the weight of (a). 0.0001 to 1% by weight.
  • the number of moles of PO added is usually 1 to 200 moles, preferably 2 to 100 moles, more preferably 3 to 30 moles per active hydrogen atom of (a0).
  • the total number of moles of AO (total of the first stage AO and the second stage PO) per active hydrogen atom of the compound constituting the residue X is usually 1 to 200 moles, preferably 3 to 100 moles. is there.
  • the number of added moles exceeds 200 moles, the viscosity of the polyoxyalkylene polyol (a) increases, and the viscosity of the mixed liquid of the polyol component (A) and the organic polyisocyanate component (B) before casting increases. .
  • q in the general formula (1) is usually 1 to 200, preferably 2 to 100, and more preferably 3 to 30.
  • p + q is usually 1 to 200, preferably 3 to 100.
  • the reaction temperature for ring-opening addition polymerization of PO is usually 0 to 250 ° C., preferably 20 to 180 ° C. From the viewpoint of controlling the reaction temperature, a method in which PO is dropped into the mixture of (a0) and TPB or a mixture of PO and TPB is dropped into (a0) is preferable.
  • the produced addition polymer contains TPB, it is adsorbed and removed using an adsorbent such as synthetic silicate (magnesium silicate and aluminum silicate) and activated clay.
  • an adsorbent such as synthetic silicate (magnesium silicate and aluminum silicate) and activated clay.
  • the total unsaturation degree (TU value) of the polyoxyalkylene polyol (a) in the present invention is usually 0.010 meq / g or less, preferably 0.005 meq / g or less, more preferably 0.003 meq / g or less.
  • TU value total unsaturation degree
  • the total degree of unsaturation can be reduced by a method of ring-opening addition polymerization of PO to the active hydrogen-containing compound (a0) in the presence of TPB.
  • the total degree of unsaturation in the present invention can be measured by the method described in JIS K 1557-3.
  • the removal of the by-product low-boiling compound (t) having a boiling point of 150 ° C. or less at normal pressure may be carried out by any generally known method. For example, the following method is mentioned. (1) A method of continuously or intermittently removing a by-product low-boiling compound (t) having a boiling point of 150 ° C. or lower at normal pressure when PO is added in the presence of a cationic catalyst. (2) A method in which (t) is decomposed and removed to a lower boiling point (u) using a catalyst (C) containing a transition metal in the fifth or sixth period of the periodic table for further reduction.
  • the catalyst (C) is a metal complex catalyst composed of a transition metal in the 5th or 6th period of the periodic table and a ligand.
  • the central metal is molybdenum, ruthenium, rhodium, palladium, silver, indium, antimony. Tungsten, iridium, platinum and the like can be used, but from the viewpoint of the catalytic activity of the catalyst (C), ruthenium, rhodium, palladium, platinum and iridium are preferable, and rhodium is more preferable.
  • the ligands that coordinate to these transition metals to form the catalyst (C) include phosphorus-containing compounds such as phosphines and phosphites, alcohols, double bond-containing compounds, and nitrogen-containing compounds such as amines and amides.
  • phosphine is preferable, more preferably trimethylphosphine, diphenylphosphinopropane, chlorodiphenylphosphinopropane and diphenylphosphinobutane, particularly preferably chlorodiphenylphosphinopropane.
  • the amount of the catalyst (C) used is not particularly limited, but is preferably 0.0001 to 10% by weight, more preferably 0.0005 to 1% by weight, based on the weight of the polyoxyalkylene polyol (a) to be produced. .
  • the by-product low-boiling compound (t) having a boiling point of 150 ° C. or less at normal pressure include formaldehyde (boiling point ⁇ 19 ° C.), acetaldehyde (boiling point 20 ° C.), propionaldehyde (boiling point 48 ° C.), and allyl alcohol.
  • formaldehyde (boiling point ⁇ 19 ° C.)
  • acetaldehyde (boiling point 20 ° C.)
  • propionaldehyde boiling point 48 ° C.
  • allyl alcohol Alternatively, 1-propenyl alcohol and an AO 1-2 mol adduct thereof can be used.
  • the low boiling point compound (u) which is a decomposition product of the by-product low boiling point compound (t) having a boiling point of 150 ° C. or lower at normal pressure, include carbon monoxide (boiling point ⁇ 192 ° C.), methane (boiling point ⁇ 162 ° C. ), Ethane (boiling point -89 ° C), butane (boiling point -0.5 ° C).
  • the content of the by-product low-boiling compound (t) having a boiling point of 150 ° C. or less at normal pressure is usually 0.020% by weight or less, preferably 0.015% by weight or less, based on the weight of the polyoxyalkylene polyol (a). More preferably, it is 0.010% by weight or less, and most preferably 0.005% by weight or less.
  • the content of (t) exceeds 0.020% by weight, the odor and non-eluting properties of the cured polyurethane resin are deteriorated, and odor and specific taste are generated in the treatment liquid by the membrane module.
  • content of the byproduct low boiling-point compound (t) in this invention can be measured on condition of the following by gas chromatography.
  • Preferred examples of (a) constituting the polyol component (A) in the present invention include propylene glycol PO adduct, polypropylene glycol (terminal secondary hydroxyl group) PO adduct, glycerin PO adduct, polyglycerin PO adduct, propylene glycol 1,2-BO adduct (terminal secondary hydroxyl group) PO adduct, glycerin 1,2-BO adduct (terminal secondary hydroxyl group) PO adduct, polyglycerin 1, Examples include 2-BO adduct (terminal secondary hydroxyl group) PO adduct and castor oil PO adduct.
  • EO adduct (b) of polyoxyalkylene polyol (a) in the present invention can be obtained by adding EO to (a) by a usual method.
  • the amount of the oxyethylene group added is 40% by weight or less, preferably 30% by weight or less, particularly preferably 10% by weight or less, based on the total weight of the oxyalkylene contained in (b).
  • the amount of the by-product low-boiling compound (t) having a total unsaturation degree and a boiling point of 150 ° C. or less at normal pressure is within the above range in (a). Inside.
  • the total unsaturation (TU value) of (b) is usually 0.010 meq / g or less, preferably 0.005 meq / g or less, more preferably 0.003 meq / g or less.
  • the total degree of unsaturation exceeds 0.010 meq / g, the physical properties of the urethane curable resin are lowered, the odor and non-elution are deteriorated, and odor and a specific taste are generated in the treatment liquid by the membrane module.
  • the content of the by-product low-boiling compound (t) having a boiling point of 150 ° C. or lower at normal pressure in (b) is usually 0.020 weight based on the weight of the polyoxyalkylene polyol EO adduct (b). % Or less, preferably 0.015% by weight or less, more preferably 0.010% by weight or less, and most preferably 0.005% by weight or less.
  • the content of (t) exceeds 0.020% by weight, the odor and non-eluting properties of the cured polyurethane resin are deteriorated, and odor and specific taste are generated in the treatment liquid by the membrane module.
  • allyl alcohol or 1-propenyl alcohol and their 1 to 2 mol adducts of AO should be particularly reduced.
  • the content of (a) and / or (b) in the polyol component (A) in the present invention is preferably 50% by weight or more, more preferably 70% by weight or more based on the weight of (A). If it is less than 50% by weight, it may be difficult to obtain the effects of the present invention.
  • the "content of (a) and / or (b)” means that (a) or (b) is used when only (a) or (b) is used. It means an amount, and when (a) and (b) are used together, it means the total amount of (a) and (b).
  • the hydroxyl value of (a) and (b) varies depending on the presence or absence of other polyols and the type of polyol used, but is usually 5 to 800 mgKOH / g, preferably 10 to 450 mgKOH / g, more preferably 30 to 300 mgKOH / g. g.
  • (A) and (b) are used in combination with other polyol [polyester polyol (f) other than castor oil-based polyol (d) and / or (d) described later]] having a relatively high molecular weight (hydroxyl value less than 400 mgKOH / g).
  • a relatively high hydroxyl value for example, 400 to 800 mgKOH / g, particularly 450 to 700 mgKOH / g is preferable.
  • the hydroxyl value can be measured by the method described in JIS K 1557-1.
  • an initiator [a compound having m active hydrogen atoms constituting the residue X in the general formula (1)] having a different type [for example, based on a polyhydric alcohol (glycerin, etc.) And those based on polyamines (ethylenediamine, etc.), those having different numbers of functional groups [m in general formula (1)] [for example, those based on bi- to trifunctional compounds (ethylene glycol, glycerin, etc.) 4-8 functional compounds (based on pentaerythritol, sorbitol, sucrose, etc.), hydroxyl value or AO addition mole number [p + q in general formula (1)] [hydroxyl value 400 mgKOH / g or more ( For example, 450 to 700 mg KOH / g) and less than 400 mg KOH / g (for example, 30 to 300 mg KOH / g)]. That.
  • the hydroxyl value is 400 mg KOH / g or more (preferably 400 to 1500 mg KOH / g) as necessary.
  • An amine polyol (c) can be used in combination.
  • the content is preferably 1% by weight or more, particularly 3 to 30% by weight, based on the weight of (A), from the viewpoint of the effect of improving fast curability.
  • Examples of the amine-based polyol (c) include hydroxyoxyalkylated products of the amino group-containing compounds (hydroxyalkyl groups having 2 to 4 or more carbon atoms), such as N, N, N ′, N′-tetrakis (2-hydroxy).
  • THPED Propyl) -ethylenediamine
  • N, N, N ′, N ′′, N ′′ -pentakis (2-hydroxypropyl) -diethylenetriamine triethanolamine, oxyalkylated products of N, N-dimethylpropylenediamine Oxyalkylated product of N, N-dimethyldipropylenetriamine (described in JP-A-11-335436), oxyalkylated product of N-aminoalkylimidazole (described in JP-A-11-322881), etc. Is mentioned.
  • THPED N, N, N ′, N ′′, N ′′ -pentakis (2-hydroxypropyl) -diethylenetriamine
  • oxyalkylated products of N, N-dimethylpropylenediamine and N-aminoalkylimidazole It is an oxyalkylated product.
  • the polyol component (A) can further contain other polyols.
  • other polyols include castor oil-based polyol (d), low-molecular-weight polyol (e), polyester polyol (f) other than (d), and mixtures of two or more thereof.
  • castor oil-based polyol (d) for example, castor oil, partially dehydrated castor oil, partially acylated castor oil, the following low molecular polyol (e) or polyoxyalkylene polyol containing (a) and castor oil Or castor oil fatty acid ester obtained by esterification with castor oil fatty acid, etc. are mentioned.
  • the hydroxyl value of (d) is usually 50 to 300 mgKOH / g, and the valence is usually 2 to 10.
  • Examples of the low molecular polyol (e) include the low molecular polyhydric alcohols exemplified as the compounds constituting X in the general formula (1) and the AO low molar adducts thereof.
  • the hydroxyl value of the low molecular polyol (e) is usually from 200 to 1,810 mgKOH / g, and the valence is usually from 2 to 20.
  • Polyester polyols (f) other than (d) include polycarboxylic acids [aliphatic saturated or unsaturated polycarboxylic acids having 4 to 40 carbon atoms (adipic acid, azelaic acid, dodecanedioic acid, maleic acid, fumaric acid, itacone Acid and dimerized linoleic acid, etc.) and / or aromatic polycarboxylic acids having 8 to 12 carbon atoms (terephthalic acid, isophthalic acid, etc.)] and polyol (the low molecular polyol (e) and / or AO adduct thereof)
  • castor oil-based polyol (d) is preferable, and castor oil is particularly preferable.
  • the amount is preferably 50% by weight or less, particularly preferably 30% by weight or less, based on the weight of the polyol component (A).
  • the ratio of each polyol in the polyol component (A) when (a) and / or (b) and (c) and / or other polyol are used in combination is the hydroxyl value of (a) and the type of polyol used in combination.
  • the amount of (a) is usually 50% by weight or more, preferably 70% by weight or more, and the amount of (b) is preferably 1% by weight or more.
  • the amount of (c) is preferably 1% by weight or more, more preferably 3 to 30% by weight, particularly preferably 3 to 20% by weight
  • the amount of (d) is preferably 1% by weight or more, more preferably 3 to 30% by weight, particularly preferably 3 to 20% by weight
  • the amount of the low molecular polyol is preferably 20% by weight or less, particularly preferably 1 to 10%.
  • polyester The amount of all preferably 1 wt% or more, particularly preferably 2 to 20 wt%.
  • At least a part of (a) is based on castor oil-based polyol (d), that is, A in general formula (1) is a residue obtained by removing active hydrogen atoms from castor oil-based polyol (d).
  • a in general formula (1) is a residue obtained by removing active hydrogen atoms from castor oil-based polyol (d).
  • the amount of (a) is usually 50% by weight or more, preferably 70% by weight. % Or more.
  • the amount of (c) in this case varies depending on whether or not (a) is amine-based [based on amines (ethylenediamine, etc.)], but is preferably 1% by weight when (a) is non-amine-based. As mentioned above, it is particularly preferably 3 to 30% by weight.
  • the amount may be smaller than the above, and a part or all of (c) in the above range may be replaced with the low molecular polyol (e). Good.
  • the amount of (a) when amine-based (a) having a relatively low molecular weight (hydroxyl value of 400 mgKOH / g or more) is used in combination with polyester polyol (f) other than (d) and / or (d) is usually 5 wt. % Or more, preferably 10 to 40% by weight, the amount of (d) is preferably 30 to 50% by weight, and the amount of the polyester polyol (f) other than (d) is preferably 30 to 50% by weight.
  • the organic polyisocyanate component (B) constituting the polyurethane resin-forming composition for a sealing material of a membrane module is an aliphatic polyisocyanate having 2 to 18 carbon atoms (excluding carbon in the NCO group, the same shall apply hereinafter).
  • Isocyanates, alicyclic polyisocyanates having 4 to 15 carbon atoms, aromatic polyisocyanates having 6 to 20 carbon atoms, araliphatic polyisocyanates having 8 to 15 carbon atoms, modified products of these polyisocyanates, and urethanes having isocyanate groups One or more compounds selected from the group consisting of prepolymers may be mentioned.
  • Examples of the aliphatic polyisocyanate having 2 to 18 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, and 2,2,4-trimethylhexaisocyanate.
  • Examples include hexanoate.
  • Examples of the alicyclic polyisocyanate having 4 to 15 carbon atoms include isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexyl diisocyanate (hydrogenated TDI), and bis (2-isocyanato). And ethyl) -4-cyclohexene-1,2-dicarboxylate, norbornane diisocyanate, and the like.
  • IPDI isophorone diisocyanate
  • MDI dicyclohexylmethane diisocyanate
  • TDI methylcyclohexyl diisocyanate
  • bis (2-isocyanato bis (2-isocyanato
  • aromatic polyisocyanate having 6 to 20 carbon atoms examples include tolylene diisocyanate (2,4-TDI, 2,6-TDI, crude TDI and a mixture thereof), diphenylmethane diisocyanate (4,4′-MDI, 2, 4'-MDI and mixtures thereof), naphthylene diisocyanate (NDI), polymethylene polyphenyl polyisocyanate and the like.
  • Examples of the araliphatic polyisocyanate having 8 to 15 carbon atoms include xylylene diisocyanate (XDI), ⁇ , ⁇ , ⁇ ′, ⁇ ′-tetramethylxylidene diisocyanate (TMXDI), diisocyanatoethylbenzene and the like.
  • modified polyisocyanate compounds include compounds in which a part or all of the isocyanate groups of the polyisocyanates exemplified above are modified to carbodiimide groups, uretdione groups, uretoimine groups, urea groups, biuret groups, isocyanurate groups, and the like. Can be mentioned.
  • Examples of the urethane prepolymer having an isocyanate group include an isocyanate group-terminated urethane prepolymer obtained by reacting an active hydrogen compound with at least one selected from the polyisocyanates exemplified above and modified products thereof.
  • Examples of the active hydrogen compound include polyoxyalkylene polyols containing (a) of the present invention, castor oil-based polyols (d), low molecular polyols (e) and (d) exemplified as other polyols in the polyol component (A). And polyester polyol (f).
  • the equivalent ratio of the NCO group in the polyisocyanate or the modified product thereof to the active hydrogen-containing group in the active hydrogen compound is usually 1.1 / 1. 100/1, preferably 2/1 to 80/1, more preferably 3/1 to 60/1.
  • the NCO group content in the urethane prepolymer is usually 3 to 35% by weight, preferably 5 to 30% by weight.
  • polyurethane resin-forming composition for a sealing material of a membrane module comprising the polyol component (A) and the organic polyisocyanate component (B) containing (a) of the present invention, depending on the application and the required degree of fast curing.
  • a urethanization catalyst (D) can be used.
  • (D) includes metal catalysts and amine catalysts.
  • Metal catalysts include tin catalysts [trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, stannous octoate, dibutyltin maleate, etc.], lead catalysts [lead oleate , Lead 2-ethylhexanoate, lead naphthenate, lead octenoate, etc.], bismuth-based catalyst [bismuth carboxylate, bismuth alkoxide, and a compound having a dicarbonyl group and bismuth, etc.], titanium-based catalyst [isopropoxy Tri-N-ethylaminoethylaminato titanium, tetrabutyl titanate, tetraisopropoxybisdioctyl phosphite titanium, etc.], iron catalysts [iron carboxylate compounds (
  • Examples of the amine catalyst include triethylenediamine, tetramethylethylenediamine, diazabicycloalkene [1,8-diazabicyclo [5,4,0] undecene-7 [DBU (manufactured by San Apro Co., Ltd., registered trademark)], etc.], dialkyl ( 1 to 3 carbon atoms) aminoalkyl (2 to 4 carbon atoms) amine [dimethylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, etc.], heterocyclic aminoalkyl (2 to 6 carbon atoms) Examples include amines [2- (1-aziridinyl) ethylamine, 4- (1-piperidinyl) -2-hexylamine and the like], and N-methyl and N-ethylmorpholine.
  • DBU diazabicycloalkene
  • DBU diazabicycloalkene
  • diazabicycloalkene bismuth-based catalyst and tin-based catalyst are preferable, and DBU, bismuth carboxylate and dibutyltin dilaurate are particularly preferable.
  • the amount of the urethanization catalyst (D) used varies depending on the application, but when high rapid curability is required, it is preferably 1,000 ppm or less, particularly preferably 10 to 100 ppm, based on the weight of the composition.
  • the NCO / active hydrogen-containing group equivalent ratio when the polyurethane resin is formed from the polyol component (A) and the organic polyisocyanate component (B) constituting the polyurethane resin-forming composition for the sealing material of the membrane module of the present invention is as follows: Usually, it is 1/5 to 5/1, preferably 1/4 to 4/1, and more preferably 1/3 to 3/1.
  • the polyurethane resin-forming composition usually comprises a combination of two components, a polyol component (A) and an organic polyisocyanate component (B).
  • a polyol component (A) and an organic polyisocyanate component (B) When the urethanization catalyst (D) is used, a combination of the three components (A), (B) and (D) may be used. Usually, a predetermined amount of (D) is previously set to (A) or (B ) Is used as a combination of two components mixed together.
  • a predetermined amount of each component of the polyurethane resin-forming composition is weighed and then reacted by mixing with a static mixer or a mechanical mixer to form a polyurethane resin.
  • the gelation time is usually 3 to 60 minutes, and complete curing requires 12 to 240 hours at room temperature.
  • the time when the hardness stops changing is regarded as complete curing (reaction end point). It is possible to shorten the time until complete curing by increasing the curing temperature (for example, 30 to 60 ° C.).
  • the hardness (ASTM D2240; 10 second value) of the cured resin obtained by reacting the polyurethane resin-forming composition is usually 45 to 100, preferably 50 to 90.
  • the viscosity of the mixed solution comprising (A) and (B) (viscosity before casting, 25 ° C.) is usually 50 to 2,000 mPa ⁇ s, preferably 100 to 1,500 mPa ⁇ s, more preferably 200 to 1, 000 mPa ⁇ s.
  • the viscosity in the present invention is measured with a B-type rotational viscometer.
  • the NCO group content in the mixed solution immediately after mixing (A) and (B) is usually 2 to 15% by weight, preferably 3 to 13% by weight.
  • the polyurethane resin-forming composition for a sealing material of a membrane module of the present invention is particularly preferably used as a sealing material for a blood treatment device and a water purifier.
  • the target blood treatment device include a hollow fiber type, membrane type or coil type artificial kidney, a clot separation module, and the like. It can also be used for artificial organs such as artificial lungs.
  • the polyol component (A) and the organic polyisocyanate component (B) are individually degassed under reduced pressure (0.1 mmHg ⁇ 2 hours). Each of these two components is weighed in a predetermined amount and then mixed, and the hollow fiber is embedded in a container by a centrifugal molding method.
  • An example of the centrifugal molding method is described in, for example, Japanese Patent Publication No. 57-58963.
  • a hollow fiber such as cellulose, acrylic, polyvinyl alcohol, polyamide or polysulfone is generally used.
  • a container made of polycarbonate, ABS, or polystyrene is used as the container.
  • the mixed solution of (A) and (B) gels 3 to 60 minutes after injection, and the module can be taken out from the molding machine.
  • curing is performed at room temperature to 60 ° C. to complete the curing.
  • the product is sterilized by steam heating for 1 hour at 121 ° C. using an autoclave to produce a product. Sterilization can also be carried out by methods other than steam heating, such as ethylene oxide gas or gamma irradiation.
  • a part shows a weight part.
  • 1,670 parts of PO through the raw material supply line was continuously charged into the liquid phase over 12 hours while controlling the reaction temperature at 70 to 80 ° C.
  • a refrigerant at ⁇ 30 ° C. was circulated in order to condense and recover PO in the condensing facility.
  • (U) which is a decomposition product of the low boiling point compound (t) having a boiling point of 150 ° C. or less at normal pressure, was removed from the exhaust system from the exhaust line so that the pressure of the reaction system did not exceed 0.6 MPa.
  • aging was performed at 70 ° C. for 4 hours, 200 parts of water was added, and the mixture was heated at 130 to 140 ° C. for 1 hour.
  • the hydroxyl value of (a-1) is 82 mgKOH / g, the viscosity is 330 mPa ⁇ s / 25 ° C., the primary rate is 73%, the total unsaturation is 0.003 meq / g, and the byproduct low boiling point compound (t) The content was 0.001% by weight.
  • polyoxyalkylene polyol (a-2) was obtained.
  • the hydroxyl value of (a-2) is 160 mgKOH / g
  • the viscosity is 260 mPa ⁇ s / 25 ° C.
  • the primary rate is 72%
  • the total unsaturation is 0.002 meq / g
  • the byproduct low boiling point compound (t) The content was 0.003% by weight.
  • ⁇ Production Example 3> In an autoclave similar to Production Example 1, 150 parts of propylene glycol and 0.09 part of TPB were charged, and stirring was then started to reduce the pressure in the autoclave and the condensation facility to 0.005 MPa. Through the raw material supply line, 2,290 parts of PO was continuously charged into the liquid phase over 12 hours while controlling the reaction temperature at 70 to 80 ° C. A refrigerant at ⁇ 30 ° C. was circulated in order to condense and recover PO in the condensing facility. Subsequently, after aging at 70 ° C. for 4 hours, 200 parts of water was added and heated at 130 to 140 ° C. for 1 hour.
  • the hydroxyl value of (a-3) is 112 mgKOH / g, the viscosity is 150 mPa ⁇ s / 25 ° C., the primary rate is 72%, the total unsaturation is 0.001 meq / g, and the byproduct low boiling point compound (t) The content was 0.003% by weight.
  • Synthetic silicate and water are added to the polyoxyalkylene polyol of Production Example 3 before the treatment, and 4.0 parts of potassium hydroxide and 1,005 parts of EO through the raw material supply line are maintained at a reaction temperature of 130 to 140 ° C. It was charged over 6 hours while controlling. Subsequently, aging was performed at 130 to 140 ° C. for 3 hours. Next, 30 parts of synthetic silicate [manufactured by Kyowa Chemical Industry Co., Ltd .; “KYOWARD 600”] and 40 parts of water were added and treated at 60 ° C. for 3 hours.
  • polyoxyalkylene polyol (b-1) After taking out from the autoclave, it was filtered through a 1 micron filter and dehydrated for 2 hours to obtain polyoxyalkylene polyol (b-1).
  • B-1) has a hydroxyl value of 78 mgKOH / g, a viscosity of 270 mPa ⁇ s / 25 ° C., a primary conversion rate of 90%, a total unsaturation of 0.001 meq / g, and a by-product low-boiling compound (t) The content was 0.003% by weight.
  • the hydroxyl value of (a′-1) is 82 mg KOH / g, the viscosity is 330 mPa ⁇ s / 25 ° C., the primary rate is 70%, the total unsaturation is 0.022 meq / g, and the by-product low-boiling compound (t) The content of was 0.031% by weight.
  • a polyoxyalkylene polyol (a′-2) was obtained in the same manner as in Comparative Production Example 1, except that the amount was 500 parts.
  • (A′-2) has a hydroxyl value of 161 mgKOH / g, a viscosity of 250 mPa ⁇ s / 25 ° C., a primary conversion rate of 71%, a total unsaturation of 0.005 meq / g, and a by-product low-boiling compound (t) The content of was 0.031% by weight.
  • (A′-3) has a hydroxyl value of 112 mgKOH / g, a viscosity of 150 mPa ⁇ s / 25 ° C., a primary conversion rate of 2%, a total unsaturation of 0.020 meq / g, and a by-product low-boiling compound (t)
  • the content of was 0.051% by weight.
  • polyoxyalkylene polyol (a′-4) was obtained.
  • (A′-4) has a hydroxyl value of 112 mgKOH / g, a viscosity of 150 mPa ⁇ s / 25 ° C., a primary conversion rate of 2%, a total unsaturation of 0.020 meq / g, and a by-product low-boiling compound (t) The content of was 0.003% by weight.
  • the hydroxyl value of (A-1) is 252 mg KOH / g, the viscosity is 610 mPa ⁇ s / 25 ° C., the total unsaturation is 0.002 meq / g, and the content of the by-product low-boiling compound (t) is 0.001% by weight.
  • the hydroxyl value of (A-2) is 310 mgKOH / g, the viscosity is 540 mPa ⁇ s / 25 ° C., the total unsaturation is 0.001 meq / g, and the content of the by-product low-boiling compound (t) is 0.002% by weight. Met.
  • the hydroxyl value of (A-3) is 274 mgKOH / g, the viscosity is 430 mPa ⁇ s / 25 ° C., the total unsaturation is 0.001 meq / g, and the content of the by-product low-boiling compound (t) is 0.002% by weight. Met.
  • the hydroxyl value of (A-4) is 275 mgKOH / g, the viscosity is 450 mPa ⁇ s / 25 ° C., the total unsaturation is 0.001 meq / g, and the content of the by-product low-boiling compound (t) is 0.002% by weight. Met.
  • the hydroxyl value of (A-6) is 259 mgKOH / g, the viscosity is 550 mPa ⁇ s / 25 ° C., the total unsaturation is 0.001 meq / g, and the content of the by-product low-boiling compound (t) is 0.002% by weight. Met.
  • an organic polyisocyanate component (B-1) comprising an NCO group-terminated urethane prepolymer.
  • (B-1) had an NCO group content of 23.2% by weight and a viscosity of 350 mPa ⁇ s / 25 ° C.
  • an organic polyisocyanate component (B-2) comprising an NCO group-terminated urethane prepolymer was obtained.
  • (B-2) had an NCO group content of 23.2% by weight and a viscosity of 200 mPa ⁇ s / 25 ° C.
  • the hydroxyl value of (A′-1) is 252 mg KOH / g, the viscosity is 610 mPa ⁇ s / 25 ° C., the total unsaturation is 0.016 meq / g, and the content of the by-product low-boiling compound (t) is 0.023 wt. %Met.
  • the hydroxyl value of (A′-2) is 310 mgKOH / g, the viscosity is 540 mPa ⁇ s / 25 ° C., the total unsaturation is 0.004 meq / g, and the content of the by-product low-boiling compound (t) is 0.023 wt. %Met.
  • the hydroxyl value of (A′-3) is 274 mg KOH / g, the viscosity is 430 mPa ⁇ s / 25 ° C., the total unsaturation is 0.016 meq / g, and the content of the by-product low-boiling compound (t) is 0.038 wt. %Met.
  • the hydroxyl value of (A′-4) is 310 mgKOH / g, the viscosity is 430 mPa ⁇ s / 25 ° C., the total unsaturation is 0.016 meq / g, and the content of the by-product low-boiling compound (t) is 0.002 wt. %Met.
  • Examples 1 to 8 and Comparative Examples 1 to 5 > Table 1 using polyol components (A-1) to (A-6) and (A'-1) to (A'-4) and organic polyisocyanate components (B-1) and (B-2)
  • the polyurethane resin-forming composition of the present invention and the comparative polyurethane resin-forming composition were obtained in the weight proportion shown in FIG.
  • Table 1 shows the results of testing the viscosity before casting of the mixture, the hardness of the cured product molded and cured, the tensile strength, the odor, the dissolution property, and the taste by the following methods.
  • the primary rate of polyoxyalkylene polyol (a) described in Example 8 in Table 1 is the same as the purification of polyoxyalkylene polyol (a-3) used in the production of polyoxyalkylene polyol (b-1). It is the value of the primary rate of the previous product.
  • ⁇ Odor of cured product> Polyol component (A) and organic polyisocyanate component (B) are uniformly mixed at 25 ° C., degassed under reduced pressure, molded into a 1 cm thick sheet, cured at 25 ° C. for 48 hours, and 10 g of cured resin is cut out. After sealing in a glass bottle with a lid and adjusting the temperature at 60 ° C. for 1 hour, the odor was judged according to the following criteria. ⁇ : No peculiar odor, ⁇ : Slight peculiar odor, ⁇ : Peculiar odor
  • ⁇ Dissolution test> The polyol component (A) and the organic polyisocyanate component (B) were uniformly mixed at 25 ° C., degassed under reduced pressure, molded into a sheet having a thickness of 1 cm, and cured at 25 ° C. for 72 hours. 10 g of a cured resin sample cut into a 1 cm square was placed in a polycup, 100 g of acetone was added, and the mixture was allowed to stand at 40 ° C. for 6 hours. The weight of the eluate obtained by drying and removing acetone from the filtrate after filtration was measured, and the elution rate was calculated from the following equation.
  • Elution rate (% by weight) (weight of eluate / weight of cured resin sample) ⁇ 100
  • ⁇ Taste test> The polyol component (A) and the organic polyisocyanate component (B) were uniformly mixed at 25 ° C., degassed under reduced pressure, molded into a sheet having a thickness of 1 cm, and cured at 25 ° C. for 72 hours. 10 g of a cured resin sample cut into a 1 cm square was placed in a glass bottle, 100 g of ultrapure water was added, and the mixture was allowed to stand at 25 ° C. for 24 hours. The ultra-pure water (blank) was used as a reference, the content liquid was filtered, and the filtrate was determined according to the following criteria. ⁇ : Taste equivalent to blank, ⁇ : Taste different from blank. As the ultrapure water, an ultrapure water production apparatus (device name: Milli-Q, manufactured by Merck & Co., Inc.) having an electric conductivity of 18.0 M ⁇ ⁇ cm or more was used.
  • the polyurethane resin-forming composition for the sealing material of the membrane module of the present invention is low in viscosity and excellent in curability, has little odor of the processing solution by the membrane module using the same, and elutes low molecular weight substances into the processing solution. Therefore, it is particularly useful as a sealing material for artificial organs such as blood treatment devices and water purifiers.
  • the cured resin obtained from the composition is excellent in electrical insulation, water resistance and adhesion to various base materials, it is used for electrical insulation such as sealing of electronic circuit boards and water-stopping such as sealing of optical fiber cable connection parts. It can also be suitably used for building materials such as adhesives for heat insulating aluminum sashes and aluminum honeycomb panels, potting materials for automobile emblems and side moldings, and laminating adhesives for various films.

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Abstract

L'objet de la présente invention concerne une composition générant une résine de polyuréthane utilisable à des fins de scellement d'un module membranaire, ladite composition présentant une faible viscosité et une remarquable capacité de durcissement, et se révélant également capable de minimiser l'odeur et le goût particulier d'un liquide traité. Ladite composition générant une résine de polyuréthane utilisable à des fins de scellement d'un module membranaire comprend (A) un composant de type polyol contenant (a) un polyoxyalkylène polyol et/ou (b) un adduit d'oxyde d'éthylène de celui-ci et (B) un composant de type polyisocyanate organique. Ladite composition est caractérisée en ce que le composant (a) porte des groupes hydroxypropyle au niveau des extrémités terminales de sa molécule; la teneur en hydroxyle primaire des groupes est supérieure ou égale à 40 %; le niveau total d'insaturation des composants (a) et (b) est inférieur ou égal à 0,010 meq/g; et la teneur en sous-produits à point d'ébullition peu élevé (t) des composants (a) et (b) est inférieure ou égale à 0,020 % en poids par rapport au poids des composants (a) et (b) respectivement, lesdits sous-produits à point d'ébullition peu élevé (t) étant des sous-produits présentant un point d'ébullition inférieur ou égal à 150 °C sous pression normale.
PCT/JP2013/056989 2012-03-29 2013-03-13 Composition générant une résine de polyuréthane utilisable à des fins de scellement d'un module membranaire WO2013146263A1 (fr)

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