JP2016138230A - Polyether polyol composition, and urethane prepolymer and polyurethane resin using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a polyether polyol composition without generating thickening or irregular thickening during an urethanization reaction.SOLUTION: There is provided a manufacturing method of a polyether polyol composition (a1) having a process 1 of removing an alkali catalyst from crude polyether polyol obtained by reacting alkylene oxide having 2 to 12 carbon atoms with a polyalcohol and/or polyphenol having 2 to 20 carbon atoms in a presence of the alkali catalyst by using an absorbent and, if needed, a filter aid to obtain purified polyether polyol, and a process 2 of adding at least one kind of acid (P) selected from a group consisting of orthophosphoric acid, phosphoric anhydride, pyrophosphoric acid, phosphorous acid and hypophosphorous acid after the process 1.SELECTED DRAWING: None

Description

  The present invention relates to a polyether polyol composition, a urethane prepolymer and a polyurethane resin using the same, and a production method thereof.

Conventionally, polyurethane resins have been used in a wide range of applications such as molding materials, paints, adhesives, sealing agents, synthetic leather, artificial leather and elastic fibers because of their excellent tensile strength and elongation properties. As a method for producing a polyether polyol used in a polyurethane resin, for example, a method for obtaining a purified polyether polyol by synthesizing a crude polyether polyol in the presence of an alkali catalyst and then removing the alkali catalyst using an adsorbent. Is known (see, for example, Patent Document 1).
However, when this purified polyether polyol is used as a polyol for urethane prepolymer or polyurethane resin, abnormal thickening may occur during the urethanization reaction depending on the type of organic polyisocyanate component.

JP-A-53-96098

  An object of the present invention is to provide a polyether polyol composition in which no thickening or abnormal thickening occurs during the urethanization reaction, and a method for producing the same.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, this invention contains the polyol (a1) which has a poly (oxyalkylene) chain | strand, water content is 2000 ppm or less, and content of a phosphate group containing compound (Q) is 0.5-20 ppm. Polyether polyol composition (A); Isocyanate group-terminated urethane prepolymer (P) obtained by reacting the polyether polyol composition (A) with an organic polyisocyanate (C); the polyether polyol composition (A) ) Containing an active hydrogen component (A) and an organic polyisocyanate (C); a process for producing the polyether polyol composition (A); the isocyanate group-terminated urethane prepolymer (P) It is a manufacturing method.

In the polyether polyol composition (A) of the present invention and the polyether polyol composition (A) obtained by the production method of the present invention, no thickening or abnormal thickening occurs during the urethanization reaction, and the urethanization reaction rate Is also appropriate.

[Polyether polyol composition (A)]
The polyether polyol composition (A) of the present invention contains a polyol (a1) having a poly (oxyalkylene) chain, and has a water content of 2000 ppm or less, preferably 1000 ppm or less, more preferably 300 ppm or less. It is. At the same time, the content of the phosphate group-containing compound (Q) is 0.5 to 20 ppm, preferably 1 to 10 ppm, and more preferably 1 to 5 ppm.
When the water content in (A) exceeds 2000 ppm, urea groups are generated, the viscosity of the isocyanate group-terminated urethane prepolymer (P) increases, and the handleability decreases.
When the content of the phosphoric acid group-containing compound (Q) in (A) is less than 0.5, the viscosity of the isocyanate group-terminated urethane prepolymer (P) increases due to the side reaction of the isocyanate, and the handling property is lowered.
When the content of the phosphoric acid group-containing compound (Q) in (A) exceeds 20 ppm, the reaction rate of the urethanization reaction decreases.
In the present invention, the phosphoric acid group-containing compound (Q) refers to at least one acid selected from the group consisting of orthophosphoric acid, phosphoric anhydride, pyrophosphoric acid, phosphorous acid and hypophosphorous acid.

The hydroxyl value of the polyol (a1) having a poly (oxyalkylene) chain is preferably 20 to 600 mgKOH / g, more preferably 25 to 300 mgKOH / g. In addition, the hydroxyl value in this invention is measured based on JISK1557-1.
The polyol (a1) having a poly (oxyalkylene) chain is a polyether polyol obtained by reacting the following polyol (a0) with an alkylene oxide having 2 to 12 carbon atoms.
As a polyol (a0), a C2-C20 polyhydric alcohol and a polyhydric phenol are mentioned.
Examples of the polyhydric alcohol having 2 to 20 carbon atoms include dihydric alcohols having 2 to 18 carbon atoms (preferably 2 to 12) [ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1 , 4- and 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, etc.], C3-C18 (preferably 3-12) C3-C5 alcohol [alkane polyol and its molecule Alternatively, intermolecular dehydrates (such as glycerin, trimethylolpropane, pentaerythritol, and diglycerin) and sugars and derivatives thereof (such as α-methylglucoside, xylitol, glucose, and fructose)] have 5 to 18 carbon atoms (preferably 5 to 12) ) 6-10 valence or it Alcohols top [alkane polyols and intramolecular or intermolecular dehydration product (dipentaerythritol, etc.), as well as sugars and derivatives thereof (sorbitol, Man'niru and sucrose, etc.), etc.], and and combinations of two or more of these.

Polyhydric phenols include dihydric phenols [monocyclic dihydric phenols (hydroquinone, etc.) and bisphenols (bisphenol A, bisphenol F, etc.), etc., trivalent to pentavalent phenols [monocyclic polyhydric phenols (pyrogallol, phloroglucin, etc.) ), 3-5 valent phenol compound formaldehyde low condensate (number average molecular weight 1000 or less) (intermediates of novolac resin and resol, etc.)], 6-10 valent or more phenol [hexavalent or more phenol compound] Formaldehyde low condensates (number average molecular weight of 1000 or less) (intermediates of novolak resins and resols, etc.), condensates of polyhydric phenols and alkanolamines (Mannich polyols), and combinations of two or more of these .

Among the polyhydric alcohols having 2 to 20 carbon atoms and polyhydric phenols, from the viewpoint of flexibility of the resin, preferred are dihydric alcohols having 2 to 18 carbon atoms, 3 to 5 alcohols having 3 to 18 carbon atoms, and A dihydric phenol, more preferably a dihydric alcohol having 2 to 12 carbon atoms and a trihydric alcohol having 3 to 12 carbon atoms, particularly preferably propylene glycol, dipropylene glycol and glycerin.
Examples of the alkylene oxide (hereinafter abbreviated as AO) of an alkylene oxide having 2 to 12 carbon atoms include AO having 2 to 12 carbon atoms, such as ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter referred to as PO). Abbreviation), 1,3-propylene oxide, 1,2-, 1,3-, 1,4- or 2,3-butylene oxide, α-olefin oxide (5 to 12 carbon atoms), styrene oxide, and these Two or more types of combination (in the case of combination, either random addition or block addition may be used).
Among AOs, AO having 2 to 4 carbon atoms is preferable from the viewpoint of physical properties of the resin, and PO is more preferable.
In particular, it contains a polyol (a1) having a poly (oxyalkylene) chain, wherein (a1) is a diol (a2) having a poly (oxyalkylene) chain, having a water content of 300 ppm or less, and phosphoric acid The polyether polyol composition (A) having a group-containing compound content of 1 to 5 ppm is preferably used as the main component (M0) for a two-component curable coating film waterproof material for use in a two-component curable coating film waterproof material. It is done.

  The diol (a2) having a poly (oxyalkylene) chain preferably has a hydroxyl value of 28 to 56, more preferably 37 to 56. In addition, the hydroxyl value in this invention is measured based on JISK1557-1.

Specific examples of (a2) are polyhydric alcohols having 2 to 20 carbon atoms and / or alkylene oxide adducts having 2 to 12 carbon atoms of polyhydric phenols, preferably 2 to 6 carbon dihydric alcohols. It is a 1,2-propylene oxide / ethylene oxide adduct of (b1).

As the dihydric alcohol (b1) having 2 to 6 carbon atoms, aliphatic diols (ethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc.) And alicyclic diols (cyclohexanediol, etc.) and araliphatic diols (catechol, resorcinol, hydroquinone, etc.).

  The addition weight of 1,2-propylene oxide / ethylene oxide is from 0 to 0.3 in terms of water resistance of the coating film, in terms of ethylene oxide weight / [(1,2-propylene oxide weight) + (ethylene oxide weight)]. It is preferable that More preferably, it is 0-0.2. (A2) contained in the main component (A) for a two-component curable coating film waterproof material may be used alone or in combination of two or more.

Of the polyether polyol composition (A), the polyol (a1) having a poly (oxyalkylene) chain is the diol (a2), the water content is 300 ppm or less, and the phosphoric acid group-containing compound is contained. A polyether polyol composition (A) having an amount of 1 to 5 ppm, a polyether polyol composition (A) having a hydroxyl value of 28 to 56, and a polyol (a1) having 2 to 2 carbon atoms. The polyether polyol composition (A), which is an alkylene oxide adduct of 6 dihydric alcohol (b1), is preferred as the main component (M0) for a two-component curable coating waterproofing material.

The main component (M0) for a two-component curable coating waterproofing material contains a diol (a2) having a poly (oxyalkylene) chain. The water content of (M0) is 300 ppm or less, preferably 280 ppm or less, more preferably 260 ppm or less, based on the weight of (M0). When the water content of (M0) is 300 ppm or less, the viscosity of the isocyanate group-terminated urethane prepolymer (P) does not increase and the handling property is good.
At the same time, the content of the phosphate group-containing compound (M0) is 1 to 5 ppm, preferably 2 to 3 ppm from the viewpoint of the urethanization reaction rate based on the weight of (M0). When the content of the phosphoric acid group-containing compound of (M0) is 1 ppm or more, the handleability of the urethane prepolymer (P) is good, and when it is 5 ppm or less, the main component (M0) for a two-component curable coating film waterproofing material And the reaction rate of urethanization with organic polyisocyanate (C) is appropriate.

As a method for setting the water content of the main component (M0) for the two-component curable coating film waterproofing material to 300 ppm or less, the temperature is 100 to 150 ° C., preferably 110 to 140 ° C., and the pressure is 133 to 6666 Pa (particularly 400 to 2666 Pa). It is preferable to dehydrate under reduced pressure.

As a method for adjusting the phosphoric acid content of the main component (M0) for a two-component curable coating film waterproof material to 1 to 5 ppm, a phosphoric acid group-containing compound is added to and mixed with the main component (M0).

The measuring method of phosphoric acid group containing compound (Q) content is measured with the following method.
The polyether polyol composition (A), ultrapure water, and n-hexane are sampled in a centrifuge tube at 10.0 g. Seal tightly and shake vigorously by hand for 5 minutes. Next, the mixture is centrifuged at 2000 rpm for 10 minutes, and after standing, the aqueous phase component is sucked out from the lower layer with a Pasteur pipette. The phosphorus content of the sucked water phase is measured with an ICP measuring device.

[Isocyanate group-terminated urethane prepolymer (P)]
The isocyanate group-terminated urethane prepolymer (P) and polyurethane resin (U) of the present invention comprise an active hydrogen component (G) containing the polyether polyol composition (A) of the present invention and an organic polyisocyanate component (C). Obtained by reaction. (A) contained in (G) may be used individually by 1 type, or may use 2 or more types together.

  The active hydrogen component (G) contains, in addition to the polyether polyol composition (A), a polymer polyol (g2) having a hydroxyl value of 600 mgKOH / g or less, a chain extender (g3), and a reaction terminator (g4). be able to. (G2), (g3) and (g4) may be used singly or in combination of two or more.

  Examples of the polymer polyol (g2) having a hydroxyl value of 600 mgKOH / g or less include polyester polyol, polyether ester polyol, polyolefin polyol, acrylic polyol, castor oil-based polyol, and polymer polyol.

  Examples of the polyester polyol include condensed polyester polyol, polylactone polyol, and polycarbonate polyol.

Condensed polyester polyols include polyhydric alcohols having 2 to 20 carbon atoms and polycarboxylic acids having 2 to 10 carbon atoms or ester-forming derivatives thereof [acid anhydrides, lower (1 to 4 carbon atoms) alkyl esters and acids. And the like obtained by condensation with a halide or the like].

Examples of the polyhydric alcohol having 2 to 20 carbon atoms include linear or branched aliphatic dihydric alcohols having 2 to 12 carbon atoms [ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentane. Linear chain such as diol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-dodecanediol, diethylene glycol, triethylene glycol and tetraethylene glycol 1,2-, 1,3- or 2,3-butanediol, 2-methyl-1,4-butanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, 2-methyl -1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,6-hexane All, 3-methyl-1,6-hexanediol, 2-methyl-1,7-heptanediol, 3-methyl-1,7-heptanediol, 4-methyl-1,7-heptanediol, 2-methyl- Branched alcohols such as 1,8-octanediol, 3-methyl-1,8-octanediol and 4-methyloctanediol]; alicyclic dihydric alcohols having 6 to 20 carbon atoms [1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclopentanediol, 1,4-cycloheptanediol, 2,5-bis (hydroxymethyl) -1,4-dioxane, 2,7 -Norbornanediol, tetrahydrofuran dimethanol, 1,4-bis (hydroxyethoxy) cyclohexane, 1,4- Sus (hydroxymethyl) cyclohexane and 2,2-bis (4-hydroxycyclohexyl) propane, etc.]; divalent alcohols having 8-20 carbon atoms [m- or p-xylylene glycol, bis (hydroxyethyl) benzene , Bis (hydroxyethoxy) benzene, bisphenol (bisphenol A, bisphenol S, bisphenol F, etc.) alkylene oxide (hereinafter abbreviated as AO) adduct (Mn less than 500), dihydroxynaphthalene AO adduct (Mn less than 500) and bis ( 2-hydroxyethyl) terephthalate and the like]; trihydric alcohol having 3 to 20 carbon atoms [aliphatic triol (such as glycerin and trimethylolpropane) and the like]; 4- to 8-valent alcohol having 5 to 20 carbon atoms [aliphatic polyol (penta Erythritol, sorbi Tol, mannitol, sorbitan, diglycerin, dipentaerythritol, etc.); saccharides (sucrose, glucose, mannose, fructose, methylglucoside and derivatives thereof)] and the like.
Among these polyhydric alcohols, from the viewpoint of tensile strength and elongation, preferred are dihydric alcohols, and more preferred are aliphatic dihydric alcohols having 2 to 8 carbon atoms. A polyhydric alcohol may be used individually by 1 type, or may use 2 or more types together.

  Examples of the polyvalent carboxylic acid having 2 to 10 carbon atoms or ester-forming derivatives thereof include aliphatic dicarboxylic acids (such as succinic acid, adipic acid, azelaic acid, sebacic acid, fumaric acid and maleic acid), and alicyclic dicarboxylic acids ( Dimer acids, etc.), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, phthalic acid, etc.), trivalent or higher polycarboxylic acids (trimellitic acid, pyromellitic acid, etc.), and their anhydrides (succinic anhydride, Maleic anhydride, phthalic anhydride, trimellitic anhydride, etc.), their acid halides (such as adipic acid dichloride), their low molecular weight alkyl esters (such as dimethyl succinate and dimethyl phthalate), and combinations thereof. . Of these, preferred are aliphatic dicarboxylic acids and ester-forming derivatives thereof. A polyvalent carboxylic acid may be used individually by 1 type, or may use 2 or more types together.

  Examples of the polylactone polyol include those obtained by ring-opening polymerization of a lactone monomer having 3 to 12 carbon atoms using the above polyhydric alcohol having 2 to 20 carbon atoms as an initiator. A lactone monomer may be used individually by 1 type, or may use 2 or more types together.

  The polycarbonate polyol is one or more (preferably 2) of the polyhydric alcohol having 2 to 20 carbon atoms (preferably an aliphatic dihydric alcohol having 3 to 9 carbon atoms, more preferably 4 to 6 carbon atoms). To 4 types) and a low molecular carbonate compound (for example, a dialkyl carbonate having 1 to 6 carbon atoms in an alkyl group, an alkylene carbonate having an alkylene group having 2 to 6 carbon atoms, and a diaryl carbonate having an aryl group having 6 to 9 carbon atoms) ) To a polycarbonate polyol produced by condensation with a dealcoholization reaction.

  As the polyether ester polyol, one or more of the polyether polyols used in the above (a1) and the polyvalent carboxylic acid having 2 to 10 carbon atoms exemplified as a raw material for the condensed polyester polyol or 1 of its ester-forming derivatives. Examples thereof include those obtained by condensation polymerization of seeds or more.

  Examples of the polyolefin polyol include polybutadiene polyol, hydrogenated polybutadiene polyol, and polyisoprene polyol.

  As the acrylic polyol, a hydroxyl group-containing ethylenically unsaturated monomer [2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc.] and other examples, for example, described in JP-A-4-292683 And a copolymer with an ethylenically unsaturated monomer. Examples of the acrylic polyol include a copolymer of hydroxyethyl acrylate and ethyl acrylate and a copolymer of hydroxyethyl acrylate, ethyl acrylate and styrene.

  Castor oil-based polyols include castor oil, castor oil fatty acid and the above-mentioned polyester polyols from polyhydric alcohols and polyoxyalkylene polyols having 2 to 20 carbon atoms (mono- or diglyceride of castor oil fatty acid, castor oil fatty acid and trimethylol). Mono-, di- or triester from propane, mono- or diester from castor oil fatty acid and polyoxypropylene glycol, etc.), those obtained by adding AO to castor oil, and mixtures of two or more of these It is done.

  Examples of the polymer polyol include one or more ethylenically unsaturated monomers (styrene, acrylonitrile, etc.) described in JP-A-4-292683 in one or more of the polymer polyol (g2). ) Polymerized and dispersed and stabilized (polymer content is usually 5 to 40% by weight).

  The hydroxyl value of the polymer polyol (g2) is usually 600 mgKOH / g or less, preferably 5 to 550 mgKOH / g, more preferably 10 to 500 mgKOH / g.

  Examples of the chain extender (g3) include water, the polyhydric alcohol having 2 to 20 carbon atoms, and a polyamine compound having a chemical formula amount of less than 500.

  Among the polyhydric alcohols having 2 to 20 carbon atoms as the chain extender (g3), the aliphatic dihydric alcohol having 2 to 8 carbon atoms and 3 having 3 to 20 carbon atoms are preferable from the viewpoint of tensile strength and elongation. And more preferred are ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, glycerin and trimethylolpropane, and particularly preferred are ethylene glycol, 1,3-propanediol and 1,4-butanediol.

  Examples of polyamine compounds having a chemical formula amount of less than 500 include aliphatic polyamines having 2 to 36 carbon atoms [alkylene diamines such as ethylenediamine and hexamethylenediamine; diethylenetriamine, dipropylenetriamine, dihexylenetriamine, triethylenetetramine, tetraethylenepentamine, Poly (n = 2-6) alkylene (carbon number 2-6) poly (n = 3-7) amine, etc.] such as pentaethylenehexamine and hexaethyleneheptamine], alicyclic polyamines having 6-20 carbon atoms ( 1,3- or 1,4-diaminocyclohexane, 4,4′- or 2,4′-dicyclohexylmethanediamine, isophoronediamine, etc.), aromatic polyamines having 6 to 20 carbon atoms (1,3- or 1,4 -Phenylenediamine, 2,4- or 2,6-tolylene diamine And 4,4'- or 2,4'-methylenebisaniline), C3-C20 heterocyclic polyamines (2,4-diamino-1,3,5-triazine, piperazine and N-aminoethyl) Piperazine, etc.), hydrazine or derivatives thereof [dibasic acid dihydrazide, etc. (adipic acid dihydrazide, etc.)] and amino alcohols having 2 to 20 carbon atoms (ethanolamine, diethanolamine, 2-amino-2-methylpropanol, triethanolamine, etc.) ) And the like. Of these, aromatic diamines having 6 to 20 carbon atoms are preferable from the viewpoint of strength and elongation of the obtained polyurethane resin, and 4,4'-diaminodiphenylmethane is more preferable.

  As the reaction terminator (g4), monoalcohols having 1 to 20 carbon atoms (methanol, ethanol, butanol, octanol, decanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, etc.) and monoamines having 1 to 20 carbon atoms. (Mono- or dialkylamines such as monomethylamine, monoethylamine, monobutylamine, dibutylamine and monooctylamine and mono- or dialkanolamines such as monoethanolamine, diethanolamine and diisopropanolamine). In addition, at least selected from the group consisting of the active hydrogen compound represented by the general formula (1), the active hydrogen compound represented by the general formula (2), and the active hydrogen compound represented by the general formula (3). One active hydrogen compound (a1) also has a function as a reaction terminator.

  As the organic polyisocyanate component (C), those conventionally used for polyurethane production can be used. Specifically, the aromatic polyisocyanate having 8 to 26 carbon atoms having 2 to 3 or more isocyanate groups ( c1), C4-C22 aliphatic polyisocyanate (c2), C8-C18 alicyclic polyisocyanate (C3), C10-C18 araliphatic polyisocyanate (c4), and poly Examples thereof include a modified product of isocyanate (c5).

  Examples of the aromatic polyisocyanate having 8 to 26 carbon atoms (c1) include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (hereinafter referred to as tolylene diisocyanate as TDI). Abbreviation), crude TDI, 4,4′- or 2,4′-diphenylmethane diisocyanate (hereinafter, diphenylmethane diisocyanate is abbreviated as MDI), crude MDI, polyarylpolyisocyanate, 4,4′-diisocyanatobiphenyl, 3, 3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4 ', 4 "-triphenyl Methane triisocyanate and m- or p-isocyanatophenylsulfonyl Cyanate and the like.

  Examples of the aliphatic polyisocyanate (c2) having 4 to 22 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2 , 2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl- 2,6-diisocyanatohexanoate is mentioned.

  Examples of the alicyclic polyisocyanate having 8 to 18 carbon atoms (c3) include isophorone diisocyanate (hereinafter abbreviated as IPDI), 4,4-dicyclohexylmethane diisocyanate (hereinafter abbreviated as hydrogenated MDI), cyclohexylene diisocyanate, and methyl. Examples include cyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.

  Examples of the araliphatic polyisocyanate (c4) having 10 to 18 carbon atoms include m- or p-xylylene diisocyanate and α, α, α ′, α′-tetramethylxylylene diisocyanate.

  The modified polyisocyanate (c5) of (c1) to (c4) is a urethane group, carbodiimide group, allohanate group, urea group, biuret group, uretdione group, uretoimine group, isocyanurate group or oxazolidone group of the polyisocyanate. And modified products [for example, modified MDI (such as urethane-modified MDI, carbodiimide-modified MDI, and trihydrocarbyl phosphate-modified MDI), urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI, and isocyanurate-modified IPDI).

  Among these, from the viewpoint of the tensile strength and elongation of the polyurethane resin, an aromatic polyisocyanate having 8 to 26 carbon atoms (c1) is more preferable, an aromatic diisocyanate having 8 to 26 carbon atoms is more preferable, and an especially preferable one is MDI. An organic polyisocyanate component (C) may be used individually by 1 type, or may use 2 or more types together.

  In the reaction of the isocyanate group-terminated urethane prepolymer (P) and the polyurethane resin (U) of the present invention, a catalyst usually used for polyurethane can be used if necessary for acceleration of the reaction. Examples of the catalyst include organometallic compounds [dibutyltin dilaurate, dioctyltin dilaurate, bismuth carboxylate, bismuth alkoxide, chelate compound of dicarbonyl group and bismuth, etc.] and inorganic metal compounds [bismuth oxide, bismuth hydroxide and halogens] Bismuth chloride, etc.]; amines [triethylamine, triethylenediamine, diazabicycloundecene, etc.] and combinations of two or more of these.

The isocyanate group-terminated urethane prepolymer (P) obtained by reacting the polyether diol composition (A1), which is the main component (M0) for the two-component curable coating film waterproof material, with the organic polyisocyanate (C) is two-component. It is preferable as the main ingredient (M) for a curable coating waterproofing material.
The two-component curable coating film waterproof material of the present invention is a diol (a2) having a poly (oxyalkylene) chain and a main component (M) for a two-component curable coating film waterproof material containing an isocyanate group-terminated urethane prepolymer (P). ) Containing a curing agent (H).

Examples of the curing agent (H) include the diol (a2) having the poly (oxyalkylene) chain. (A2) may be used alone or in combination of two or more.

  The main component (M) and the curing agent (H) for waterproofing the two-component curable coating film of the present invention include a filler (filler), a colorant, a curing accelerating catalyst, a plasticizer, a diluent (thickening agent), and an antioxidant. Further, additives such as an ultraviolet absorber, an anti-sagging agent, and a surface modifier can be contained. The filler (filler) and the colorant are preferably contained in the curing agent (H) from the viewpoint of storage stability.

  Examples of the filler (filler) include clay, heavy calcium carbonate, calcium carbonate surface-treated with fatty acid, barium sulfate, alumina, silica, carbon black, calcium oxide, titanium oxide, diatomaceous earth, glass fiber and crushed materials thereof ( Cut glass, milled glass, glass flakes, etc.), talc, mica, shirasu balloon and other inorganic fillers.

Examples of the colorant include pigments such as inorganic pigments and organic pigments, and dyes.
Examples of inorganic pigments include chrome yellow, zinc yellow, bitumen, barium sulfate, cadmium red, titanium oxide, zinc white, bengara, alumina, calcium carbonate, ultramarine blue, carbon black, graphite, and titanium black.

  Organic pigments include β-naphthol, β-oxynaphthoic acid anilide, acetoacetanilide, pyrazolone and other soluble azo pigments, β-naphthol, β-oxynaphthoic acid, β-oxynaphthoic acid Insoluble azo pigments such as anilide, acetoacetanilide monoazo, acetoacetate anilide disazo, pyrazolone, phthalocyanine pigments such as copper phthalosinine blue, halogenated copper phthalocyanine blue, sulfonated copper phthalocyanine blue, metal-free phthalocyanine, iso Examples thereof include polycyclic or heterocyclic compounds such as sindrinone, quinacridone, dioxazine, perinone, and perylene.

  Specific examples of dyes include yellow dyes, aryl or heteryl azo dyes having phenols, naphthols, anilines, pyrazolones, pyridones or open-chain active methylene compounds as coupling components, open-chain activity as coupling components Examples thereof include azomethine dyes having a methylene compound, methine dyes such as benzylidene dyes and monomethine oxonol dyes, quinone dyes such as naphthoquinone dyes and anthraquinone dyes, quinophthalone dyes, nitro, nitroso dyes, acridine dyes and acridinone dyes.

  For magenta dyes, phenols, naphthols, anilines, pyrazolones, pyridones, pyrazolotriazoles, ring-closing active methylene compounds or heterocycles (pyrrole, imidazole, thiophene and thiazole derivatives, etc.) are used as coupling components. Aryl or heteryl azo dyes, azomethine dyes having a pyrazolone or pyrazolotriazole as a coupling component, arylidene dyes, styryl dyes, merocyanine dyes such as merocyanine dyes and oxonol dyes, diphenylmethane dyes, triphenylmethane dyes and xanthene dyes Examples thereof include carbonium dyes, quinone dyes such as naphthoquinone, anthraquinone and anthrapyridone, and condensed polycyclic dyes such as dioxazine dyes.

  As cyan dyes, azomethine dyes such as indoaniline dyes and indophenol dyes, polymethine dyes such as cyanine dyes, oxonol dyes and merocyanine dyes, carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes, phthalocyanine dyes, anthraquinone dyes Examples of coupling components include phenols, naphthols, anilines, pyrrolopyrimidinone or pyrrolotriazinone derivatives, aryl or heteryl azo dyes (such as CI Direct Blue 14), and indigo / thioindigo dyes.

  Examples of the curing accelerating catalyst include the catalyst used in the production of the isocyanate group-terminated urethane prepolymer and a combination of two or more of these.

  Examples of the plasticizer include ester plasticizers [dibutyl phthalate, dioctyl phthalate, dioctyl adipate and polyethylene glycol (number average molecular weight: 200) diadipate, etc.], tar plasticizers (tar and asphalt, etc.) and petroleum resin plasticizers. It is done.

  Diluents (and thickeners) include aliphatic hydrocarbons such as n-hexane and n-heptane, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate, butyl acetate and cellosolve, acetone And solvents such as ketones such as methyl ethyl ketone and ethers such as diethylene glycol dimethyl ether and ethylene glycol dibutyl ether. The content is preferably 0 to 20% by weight based on the total weight of the main agent and the curing agent in the case of the two-component curable type, and based on the weight of the urethane prepolymer having an isocyanate group at the terminal in the case of the one-component curable type. More preferably, it is 0 to 5% by weight.

Antioxidants include hindered phenolic antioxidants [Irganox 1010 and Irganox 1076 (both manufactured by BASF Japan), etc.] and hindered amine antioxidants [Sanol LS770 and Sanol LS-744 (both manufactured by Sankyo). )].
Examples of the ultraviolet absorber include triazole-based ultraviolet absorbers [Tinuvin 320 (manufactured by BASF Japan), etc.] and benzophenone-based ultraviolet absorbers [Siasorb UV9 (manufactured by Cyanamid), etc.].
Examples of the sag-preventing agent include hydrogenated castor oil compounds, calcium stearate, aluminum stearate, barium stearate and the like.

There is no particular limitation on the timing of addition of the additive, and it may be added to the main agent (M) and / or the curing agent (H) in advance, or added when mixing (M) and (H). May be.

  As an example of how to use the two-component curable urethane coating waterproof material, the main agent (M), the curing agent (H) and additives as necessary are mixed at the construction site, and in some cases a primer is applied to the coated surface in advance. After the application, the mixture is applied by a method such as spraying, and after the application, the surface of the application surface is finished using a spatula or the like and cured until the curing is completed.

  The main agent (M) and the curing agent (H) are usually mixed at room temperature and used immediately after mixing. Mixing is preferably performed with a mixer or the like.

[Production method]
The method for producing the polyether polyol composition (A) in the present invention is an adsorbent and, if necessary, a crude polyether polyol obtained by reacting an alkylene oxide having 2 to 12 carbon atoms with the polyol (a0) in the presence of an alkali catalyst. It has the process 1 which removes an alkali catalyst using a filter aid, dehydrates, and obtains purified polyether polyol, and the process 2 which adds a phosphoric acid group containing compound (Q) after the said process 1.

  The addition reaction of AO can be carried out under ordinary reaction conditions using a conventionally known ordinary alkali catalyst. Alkali catalysts include alkali metal hydroxides (potassium hydroxide, sodium hydroxide, cesium hydroxide, etc.), alkali metal alcoholates (sodium methylate, potassium methylate, etc.), alkali metal simple substances (metal potassium, etc.), alkali metals Examples thereof include carbonates (such as potassium carbonate and sodium carbonate) and mixtures of two or more thereof. Among these, from the viewpoint of productivity, preferred is an alkali metal hydroxide, and more preferred is potassium hydroxide.

  The adsorbent and the filter aid are not particularly limited as long as they are usually used, and oxides of one or more elements selected from Group 1, Group 2, Group 13, and Group 14 or Examples include hydroxides, complex salts of one or more elements selected from Group 1, Group 2, Group 13 and Group 14, silicates, and natural products containing these, and combinations of two or more May be.

Examples of Group 1 elements constituting the compound include sodium and potassium. Examples of Group 2 elements include magnesium, calcium, and barium. Examples of the Group 13 element include aluminum. Examples of the Group 14 element include silicon.
Specifically, examples of the oxide of one or more elements selected from Group 1, Group 2, Group 13, and Group 14 include MgO and Al ₂ O ₃ . Examples of the hydroxide of one or more elements selected from Group 1, Group 2, Group 13, and Group 14 include Al (OH) ₃ .xH ₂ O. Examples of complex salts of one or more elements selected from Group 1, Group 2, Group 13 and Group 14 include Mg ₄ . ₅ Al ₂ (OH) ₁₃ CO ₃ .3.5H ₂ O, Mg ₀ . ₇ Al ₀ . ₃ O ₁ . ₁₅ , Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O and Mg ₀ . ₇ Al ₀ . ₃ O ₁ . ₁₅ etc. are mentioned. Examples of the silicate include synthetic magnesium silicate and synthetic aluminum silicate. Diatomaceous earth etc. are mentioned as a natural product containing these.

  Preferred as the adsorbent is an oxide or hydroxide of one or more elements selected from Group 1, Group 2 and Group 13 and one type selected from Group 1, Group 2 and Group 13. A complex salt of the above elements, more preferably a complex salt of one or more elements selected from Group 2 and Group 13.

  Preferred as filter aids are oxides or hydroxides of Group 14 elements, complex salts containing at least Group 14 elements and optionally Group 2 and / or Group 13 elements, and diatomaceous earth It is.

  The weight ratio of the adsorbent to the filter aid (adsorbent: filter aid) is preferably 5:95 to 100: 0, and more preferably 15:85 to 90:10.

  The amount of adsorbent used relative to the crude polyether polyol is preferably 0.05 to 3.0% by weight. The lower limit is more preferably 0.1% by weight, particularly preferably 0.15% by weight, and the upper limit is more preferably 1.5% by weight, particularly preferably 0.85% by weight. When the amount of the adsorbent used is 1% by weight or less, filterability is good, and when it is 0.05% by weight or more, alkali removal is good.

  The amount of filter aid used relative to the crude polyether polyol is preferably 0 to 0.8% by weight. The lower limit is more preferably 0.05% by weight, particularly preferably 0.1% by weight, and the upper limit is more preferably 0.75% by weight, particularly preferably 0.65% by weight. When the amount of the filter aid used is 0.8% by weight or less, metal elution is small in the polyether.

The adsorbent particles preferably have a ratio of particles of 75 μm or less of 50% or more, more preferably 60% or more, and particularly preferably 70% or more.
The proportion of particles of filter aid is preferably 60% or more, more preferably 70% or more, and particularly preferably 80% or more.

  As a condition for treating with an adsorbent and, if necessary, a filter aid, the treatment temperature may be room temperature or under heating, preferably 5 to 150 ° C, more preferably 15 to 100 ° C. The treatment time is preferably 15 to 120 minutes, more preferably 20 to 80 minutes. The treatment is preferably performed with stirring in a treatment tank. The adsorption and, if necessary, the treatment with a filter aid may be performed a plurality of times.

  In the purification method of the present invention, low molecular weight substances may be removed by washing with water if necessary after adsorption and treatment with a filter aid if necessary. The amount of water added when washing with water is preferably 5 to 80% by weight, more preferably 10 to 50% by weight, based on the crude polyether polyol. Washing with water is preferably performed at normal pressure or under pressure at 5 to 150 ° C. (particularly 15 to 140 ° C.).

  The polyether obtained by the purification method of the present invention has a low water content depending on applications such as for polyurethane resins. Therefore, if necessary, dehydration is performed before and / or after the treatment with the adsorbent and the filter aid. When dehydrating, dehydrating under reduced pressure at 100 to 150 ° C. (especially 110 to 140 ° C.) and 133 to 6666 Pa (especially 400 to 2666 Pa).

  From the crude polyether after the adsorption and treatment with a filter aid, if necessary, the purified polyether is removed by removing the filter aid or the like, for example, by filtration (preferably pressure filtration) or centrifugation. Can be obtained.

    The manufacturing method of the polyether polyol composition (A) of this invention has the process 2 which mixes a phosphate group containing compound (Q) after the said process 1. FIG.

  The addition amount of (Q) in the polyether polyol composition (A) is preferably 20.0 ppm or less from the viewpoint of the reaction rate of urethanization based on the weight of the polyether polyol composition (a1). From the viewpoint of handling properties, it is 0.5 ppm or more, more preferably 1.0 to 10.0 ppm, and particularly preferably 1.0 to 5.0 ppm.

Although it does not specifically limit as a manufacturing method of the isocyanate group terminal urethane prepolymer (P) of this invention, For example, active hydrogen content of polyether polyol composition (A) and (A) in presence or absence of an organic solvent is included. Examples include a method of mixing and heating the amount of (C) in which the equivalent of the isocyanate group is excessive with respect to the equivalent of the group.
The equivalent ratio of the isocyanate group of (C) to the active hydrogen group of (A) (equivalent of isocyanate group / equivalent of active hydrogen group) is usually 1.5 to 3.0, from the viewpoint of the viscosity of the prepolymer. , Preferably 1.8 to 2.5.

The production method of the polyurethane resin of the present invention is not particularly limited, but a urethane prepolymer having an isocyanate group and preferably an organic solvent are continuously line-mixed with a static mixer, and further this urethane prepolymer and chain are mixed with an instantaneous mixer. Examples thereof include a method of instantaneously mixing and reacting with an extender, a method of batch-reacting (A), (B), and, if necessary, an organic solvent in a batch, and a reaction of heating.
The equivalent ratio of the isocyanate group of (C) and the active hydrogen group of (A) (equivalent of isocyanate group / equivalent of active hydrogen group) is usually 0.8 to 2.0, from the viewpoint of resin moldability, Preferably it is 0.9-1.5.

  In the production method of the isocyanate group-terminated urethane prepolymer (P) or polyurethane resin (U) of the present invention, an organic solvent can be used in any production process. The organic solvent is not particularly limited, and examples thereof include ketone solvents having 3 to 10 carbon atoms (for example, acetone, methyl ethyl ketone and methyl isobutyl ketone), and ester solvents having 2 to 10 carbon atoms (for example, ethyl acetate, butyl acetate and γ-butyrolactone). ), C 4-10 ether solvents (eg, dioxane, tetrahydrofuran, ethyl cellosolve and diethylene glycol dimethyl ether), C 3-10 amide solvents [eg, N, N-dimethylformamide, N, N-dimethylacetamide, N -Methyl-2-pyrrolidone and N-methylcaprolactam], a sulfoxide solvent having 2 to 10 carbon atoms (for example, dimethyl sulfoxide), an alcohol solvent having 1 to 8 carbon atoms (for example, methanol, ethanol, isopropyl alcohol and octano). ) And hydrocarbon solvent (e.g., n- butane having 4 to 10 carbon atoms, cyclohexane, toluene and xylene) and the like.

When an organic solvent is used, the amount used is preferably such that the concentration of the urethane prepolymer (P) or polyurethane resin (U) is 10 to 90% by weight, more preferably 30 to 80% by weight. .

  The production of the urethane prepolymer (P) or the polyurethane resin (U) can be carried out under conventionally known ordinary reaction conditions. The catalyst used for the reaction of the above isocyanate group-terminated urethane prepolymer and these as necessary for promoting the reaction These two or more types are used in combination.

Pigments, stabilizers and other additives (such as anti-fusing agents and flame retardants) can be added to the urethane prepolymer (P) and the polyurethane resin (U) of the present invention.
The pigment is not particularly limited, and known organic pigments and / or inorganic pigments can be used. Examples of the organic pigment include insoluble azo pigments, soluble azo pigments, copper phthalocyanine pigments, and quinacridone pigments. Examples of inorganic pigments include chromates, ferrocyan compounds, metal oxides, selenium sulfide compounds, metal salts (sulfates, silicates, carbonates, phosphates, etc.), metal powders, and carbon black. The amount of the pigment used is usually 0 to 5% by weight, preferably 0.1 to 3% by weight, based on the weight of the polyurethane resin.

A stabilizer is not specifically limited, A well-known antioxidant and / or a ultraviolet absorber can be used.
Antioxidants include phenolic [2,6-di-t-butyl-p-cresol and butylated hydroxyanisole, etc.]; bisphenol [2,2′-methylenebis (4-methyl-6-t-butylphenol) Etc.]; phosphorus-based [triphenyl phosphite and diphenylisodecyl phosphite etc.] and the like. Examples of the ultraviolet absorber include benzophenone [2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone and the like]; benzotriazole [2- (2′-hydroxy-5′-methylphenyl) benzotriazole and the like]; Salicylic acid type [phenyl salicylate and the like]; hindered amine type [bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like] and the like. The usage-amount of a stabilizer is 0-5 weight part normally based on the weight of a polyurethane resin, Preferably it is 0.1-3 weight%.

  The pigment, stabilizer and other additives can be added at any stage during the production of the polyurethane resin (U), and may be added after the production.

Although it does not specifically limit as a manufacturing method of the 2 liquid-curing type coating-film waterproof material of this invention, For example, the equivalent of an isocyanate group is equivalent to the equivalent of active hydrogen containing groups, such as (a2) in (H) and (H). Examples include a method of mixing an equivalent amount of (P).

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following, parts represent parts by weight.

Example 1 [Production of polyether polyol composition (A-1)]
In a reaction vessel equipped with a stirrer and a temperature controller, 13.8 parts of glycerin and 1.9 parts of potassium hydroxide were charged, and 736.2 parts of PO was added dropwise over 12 hours at a reaction temperature of 90 to 110 ° C., and then 6 hours. Aging was carried out to obtain 750 parts of a crude polyether polyol. To 750 parts of the obtained crude polyether polyol, 15 parts of synthetic silicate [KYOWARD 600 (manufactured by Kyowa Chemical Industry Co., Ltd.)] and 15 parts of water were added, treated at 90 ° C. for 3 hours, and filtered through a 1 μm filter. 700 parts of a polyol (a1-1) having a purified poly (oxyalkylene) chain having a water content of 500 ppm and a hydroxyl value of 33.7 mgKOH / g, dehydrated at 130 ° C. and a pressure of 6.7 kPa or less for 2 hours. Got. 700 parts of the obtained purified polyol (a1-1) and 0.0035 parts of orthophosphoric acid [manufactured by Wako Pure Chemical Industries, Ltd.] were mixed to obtain a polyether polyol composition (A-1).

Example 2 [Production of Polyether Polyol Composition (A-2)]
In a reaction vessel equipped with a stirrer and a temperature controller, 28.5 parts of propylene glycol and 1.9 parts of potassium hydroxide were charged, and 721.5 parts of PO were added dropwise over 12 hours at a reaction temperature of 90 to 110 ° C. Aging with time yielded 750 parts of crude polyether polyol. To 750 parts of the obtained crude polyether polyol, 15 parts of synthetic silicate [KYOWARD 600 (manufactured by Kyowa Chemical Industry Co., Ltd.)] and 15 parts of water were added, treated at 90 ° C. for 3 hours, and filtered through a 1 μm filter. Thereafter, polyol (a1-2) 700 having a purified poly (oxyalkylene) chain having a water content of 500 ppm and a hydroxyl value of 33.7 mgKOH / g was dehydrated at 130 ° C. and a pressure of 6.7 kPa or less for 2 hours. Got a part. 700 parts of the obtained purified polyol (a1-2) and 0.0035 parts of orthophosphoric acid [manufactured by Wako Pure Chemical Industries, Ltd.] were mixed to obtain a polyether polyol composition (A-2).

Example 3 [Production of Polyether Polyol Composition (A-3)]
In a reaction vessel equipped with a stirrer and a temperature controller, 28.5 parts of propylene glycol and 1.1 parts of potassium hydroxide were charged, and 422.0 parts of PO was dropped at a reaction temperature of 90 to 110 ° C. over 12 hours. Aging was conducted for a period of time to obtain 450.5 parts of a crude polyether polyol. To 450.5 parts of the obtained crude polyether polyol, 9 parts of synthetic silicate [KYOWARD 600 (manufactured by Kyowa Chemical Industry Co., Ltd.)] and 9 parts of water were added and treated at 90 ° C. for 3 hours, with a 1 μm filter. Polyol (a1-3) having a purified poly (oxyalkylene) chain having a water content of 500 ppm and a hydroxyl value of 56.1 mgKOH / g after dehydration at 130 ° C. and a pressure of 6.7 kPa or less after filtration. 400 parts were obtained. 400 parts of the obtained purified polyol (a1-3) and 0.0020 part of orthophosphoric acid [manufactured by Wako Pure Chemical Industries, Ltd.] were mixed to obtain a polyether polyol composition (A-3).

Example 4 [Production of Polyether Polyol Composition (A-4)]
A polyether polyol composition (A-4) was obtained in the same manner as in Example 1 except that the raw material orthophosphoric acid was changed to phosphoric anhydride [manufactured by Wako Pure Chemical Industries, Ltd.].

Example 5 [Production of Polyether Polyol Composition (A-5)]
A polyether polyol composition (A-5) was obtained in the same manner as in Example 2 except that orthophosphoric acid as a raw material was changed to phosphoric anhydride [manufactured by Wako Pure Chemical Industries, Ltd.].

Example 6 [Production of polyether polyol composition (A-6)]
A polyether polyol composition (A-6) was obtained in the same manner as in Example 1 except that orthophosphoric acid as a raw material was changed to pyrophosphoric acid [manufactured by Wako Pure Chemical Industries, Ltd.].

Example 7 [Production of polyether polyol composition (A-7)]
A polyether polyol composition (A-7) was obtained in the same manner as in Example 2 except that orthophosphoric acid as a raw material was changed to pyrophosphoric acid [manufactured by Wako Pure Chemical Industries, Ltd.].

Example 8 [Production of polyether polyol composition (A-8)]
A polyether polyol composition (A-8) was obtained in the same manner as in Example 2 except that the amount of orthophosphoric acid as a raw material was changed to 0.0004 part.

Example 9 [Production of polyether polyol composition (A-9)]
A polyether polyol composition (A-9) was obtained in the same manner as in Example 3 except that the amount of orthophosphoric acid as a raw material was changed to 0.0002 part.

Example 10 [Production of Polyether Polyol Composition (A-10)]
A polyether polyol composition (A-10) was obtained in the same manner as in Example 2 except that the amount of orthophosphoric acid as a raw material was changed to 0.0140 part.

Example 11 [Production of Polyether Polyol Composition (A-11)]
A polyether polyol composition (A-11) was obtained in the same manner as in Example 3 except that the amount of orthophosphoric acid as a raw material was changed to 0.0080 part.

Example 12 [Production of Polyether Polyol Composition (A-12)]
A polyether polyol composition (A-12) was obtained in the same manner as in Example 2 except that the dehydration time was changed to 1 hour.

Example 13 [Production of polyether polyol composition (A-13)]
A polyether polyol composition (A-13) was obtained in the same manner as in Example 3 except that the dehydration time was changed to 1 hour.

Comparative Example 1 [Production of Comparative Polyether Polyol Composition (A′-14)]
A comparative polyether polyol composition (A′-14) was obtained in the same manner as in Example 2 except that the amount of orthophosphoric acid as a raw material was changed to 0.0210 parts.

Comparative Example 2 [Production of Comparative Polyether Polyol Composition (A′-15)]
A comparative polyether polyol composition (A′-15) was obtained in the same manner as in Example 3 except that the amount of orthophosphoric acid as a raw material was changed to 0.0120 part.

Comparative Example 3 [Production of Comparative Polyether Polyol Composition (A′-16)]
A comparative polyether polyol composition (A′-16) was obtained in the same manner as in Example 2 except that the dehydration time was changed to 0.5 hour.

Comparative Example 4 [Production of Comparative Polyether Polyol Composition (A′-17)]
A comparative polyether polyol composition (A′-17) was obtained in the same manner as in Example 3 except that the dehydration time was changed to 0.5 hour.

Example 14 [Production of Urethane Prepolymer (P-1)]
In the reaction vessel, 71.4 parts of polyether polyol composition (A-1) as active hydrogen component (A) and 28.6 parts of (A-2) and 4,4′- as organic polyisocyanate component (C) Diphenylmethane diisocyanate (13.4 parts) was charged and reacted at 70 ° C. for 18 hours to obtain a urethane prepolymer (P-1). The viscosity of the urethane prepolymer (P-1) measured using a B-type viscometer [BH or BL-type viscometer manufactured by Toki Sangyo Co., Ltd.] after 12 hours of reaction is 7.5 Pa. -The viscosity at 25 degreeC after 18 hours of reaction time was 9.2 Pa.s.

Examples 15 to 20 and Comparative Examples 5 to 8 [Production of Urethane Prepolymers (P-2) to (P-7) and Comparative Examples of Urethane Prepolymers (P′-1) to (P′-4))
The urethane prepolymers (P-2) to (P-7) and the urethane prepolymers (P′-1) to (P′−) of the comparative examples were the same as in Example 14 except that the raw materials listed in Table 1 were used. 4) was obtained. 25 ° C. after 12 hours and 18 hours after the reaction time of the obtained urethane prepolymers (P-2) to (P-7) and the urethane prepolymers (P′-1) to (P′-4) of Comparative Examples Table 1 shows the viscosity.

When Examples 14-16 containing trifunctional polyol are compared with Comparative Example 5, in Examples 14-16, the viscosity is only slightly increased, but the addition amount of the phosphate group-containing compound (Q) is 0.1. In Comparative Example 5, which is less than 5 ppm, the viscosity is abnormally increased.
When Example 17 containing bifunctional polyol and Comparative Example 6 are compared, Comparative Example 6 in which the addition amount of the phosphate group-containing compound (Q) is less than 0.5 ppm is not much different from that of trifunctional polyol. However, the viscosity is still higher than in Example 17 and the handling properties are worse.
Comparing Example 18 containing bifunctional polyol and Comparative Example 7, in Comparative Example 7 in which the addition amount of the phosphate group-containing compound (Q) exceeds 20 ppm, the viscosity increased from 12 hours to 18 hours. It can be seen that the reaction rate is slow and the reaction is not completed.
When Example 17 containing bifunctional polyol and Comparative Example 8 are compared, Comparative Example 8 having a water content of more than 2000 ppm is not much different from Trifunctional polyol, but the viscosity is still higher than Example 17 and handling. Sex is getting worse.

Next, examples in which the polyether polyol composition (A) and the isocyanate group-terminated urethane prepolymer (P) using the polyether polyol composition (A) are used for a two-component curable coating waterproofing material will be described.

Example 21 [Production of polyether polyol composition (A-18)]
A reaction vessel equipped with a stirrer and a temperature controller was charged with 50.4 mol 1,2-propylene oxide adduct (a1-4) of propylene glycol, dehydrated at 130 ° C. and a pressure of 6.7 kPa or less for 3 hours, 700 parts of 50.4 mol 1,2-propylene oxide adduct of purified propylene glycol having a content of 200 ppm and a hydroxyl value of 37.4 were obtained. 700 parts of 50.4 mol 1,2-propylene oxide adduct of purified propylene glycol and 0.0014 part of orthophosphoric acid [manufactured by Wako Pure Chemical Industries, Ltd.] were mixed to obtain a polyether polyol composition (A- 18) was obtained.

Example 22 [Production of polyether polyol composition (A-19)]
A reaction vessel equipped with a stirrer and a temperature controller was charged with 33.4 mol of 1,2-propylene oxide adduct (a1-5) of ethylene glycol, dehydrated at 130 ° C. and a pressure of 6.7 kPa or less for 3 hours, 700 parts of 33.4 mol 1,2-propylene oxide adduct of purified ethylene glycol having a content of 200 ppm and a hydroxyl value of 56 were obtained. 700 parts of the obtained 33.4 mol 1,2-propylene oxide adduct of purified ethylene glycol and 0.0014 parts of orthophosphoric acid [manufactured by Wako Pure Chemical Industries, Ltd.] were mixed to obtain a polyether polyol composition (A- 19) was obtained.

Example 23 [Production of polyether polyol composition (A-20)]
A reaction vessel equipped with a stirrer and a temperature controller was charged with 50.4 mol 1,2-propylene oxide adduct (a1-4) of propylene glycol and dehydrated at 130 ° C. and a pressure of 6.7 kPa or less for 2.5 hours. Then, 700 parts of 50.4 mol 1,2-propylene oxide adduct of purified propylene glycol having a water content of 300 ppm and a hydroxyl value of 37.4 was obtained. 700 parts of 50.4 mol 1,2-propylene oxide adduct of purified propylene glycol and 0.0014 part of orthophosphoric acid [manufactured by Wako Pure Chemical Industries, Ltd.] were mixed to obtain a polyether polyol composition (A- 20) was obtained.

Example 24 [Production of Polyether Polyol Composition (A-21)]
A reaction vessel equipped with a stirrer and a temperature controller is charged with 33.4 mol of 1,2-propylene oxide adduct (a1-5) of ethylene glycol and dehydrated at 130 ° C. and a pressure of 6.7 kPa or less for 2.5 hours. Then, 700 parts of a 33.4 mol 1,2-propylene oxide adduct of purified ethylene glycol having a water content of 300 ppm and a hydroxyl value of 56 was obtained. 700 parts of the obtained 33.4 mol 1,2-propylene oxide adduct of purified ethylene glycol and 0.0014 parts of orthophosphoric acid [manufactured by Wako Pure Chemical Industries, Ltd.] were mixed to obtain a polyether polyol composition (A- 21) was obtained.

Example 25 [Production of polyether polyol composition (A-22)]
A polyether polyol composition (A-22) was obtained in the same manner as in Example 21 except that the amount of orthophosphoric acid as a raw material was changed to 0.0007 part.

Example 26 [Production of polyether polyol composition (A-23)]
A polyether polyol composition (A-23) was obtained in the same manner as in Example 22 except that the amount of orthophosphoric acid as a raw material was changed to 0.0007 part.

Example 27 [Production of polyether polyol composition (A-24)]
A polyether polyol composition (A-24) was obtained in the same manner as in Example 21 except that the amount of orthophosphoric acid as a raw material was changed to 0.0035 part.

Example 28 [Production of polyether polyol composition (A-25)]
A polyether polyol composition (A-25) was obtained in the same manner as in Example 22 except that the amount of orthophosphoric acid as a raw material was changed to 0.0035 part.

Example 29 [Production of polyether polyol composition (A-26)]
A polyether polyol composition (A-26) was obtained in the same manner as in Example 23 except that the amount of orthophosphoric acid as a raw material was changed to 0.0007 part.

Example 30 [Production of polyether polyol composition (A-27)]
A polyether polyol composition (A-27) was obtained in the same manner as in Example 24 except that the amount of orthophosphoric acid as a raw material was changed to 0.0007 part.

Example 31 [Production of Polyether Polyol Composition (A-28)]
A polyether polyol composition (A-28) was obtained in the same manner as in Example 23 except that the amount of orthophosphoric acid as a raw material was changed to 0.0035 part.

Example 32 [Production of Polyether Polyol Composition (A-29)]
A polyether polyol composition (A-29) was obtained in the same manner as in Example 24 except that the amount of orthophosphoric acid as a raw material was changed to 0.0035 part.

Example 33 [Production of polyether polyol composition (A-30)]
A polyether polyol composition (A-30) was obtained in the same manner as in Example 21 except that the dehydration time was changed to 2 hours.

Example 34 [Production of Polyether Polyol Composition (A-31)]
A polyether polyol composition (A-31) was obtained in the same manner as in Example 22 except that the dehydration time was changed to 2 hours.

Example 35 [Production of polyether polyol composition (A-32)]
A polyether polyol composition (A-32) was obtained in the same manner as in Example 21 except that the amount of orthophosphoric acid as a raw material was changed to 0.0049 part.

Example 36 [Production of polyether polyol composition (A-33)]
A polyether polyol composition (A-33) was obtained in the same manner as in Example 22 except that the amount of orthophosphoric acid as a raw material was changed to 0.0049 part.

Example 37 [Production of isocyanate group-terminated urethane prepolymer (P-8)]
In a reaction vessel, 71.4 parts of polyether polyol composition (A-18) as active hydrogen component and 28.6 parts of (A-19) and 4,4′-diphenylmethane diisocyanate as organic polyisocyanate (C) 13. 4 parts were charged and reacted at 70 ° C. for 12 hours to obtain an isocyanate group-terminated urethane prepolymer (P-8). The isocyanate group content of the isocyanate group-terminated urethane prepolymer (P-8) after 6 hours and 12 hours was 1.4% and 1.1%, respectively. The viscosity at 25 ° C. of the isocyanate group-terminated urethane prepolymer (P-8) after 12 hours was 5500 mPa · s. In addition, the isocyanate group content rate in this invention was measured based on JISK7301 and a viscosity based on JISK7117-1.

Examples 38 to 44 [Production of isocyanate group-terminated urethane prepolymers (P-9) to (P-15)]
Except having replaced with the raw material of Table 2, it carried out similarly to Example 37, and obtained the isocyanate group terminal urethane prepolymer (P-9)-(P-15). Table 2 shows the isocyanate group content of the obtained isocyanate group-terminated urethane prepolymers (P-9) to (P-15) after 6 hours and 12 hours and the viscosity at 25 ° C. after 12 hours of reaction. It was shown to.

<Method for measuring moisture>
Moisture is measured according to JIS K 1557-2.
<Measurement method of phosphate group-containing compound content>
The measuring method of phosphate group containing compound content is measured with the following method.
A main component component (A) for two-component curable coating film waterproofing material, ultrapure water, and n-hexane are sampled in a centrifuge tube at 10.0 g. Seal tightly and shake vigorously by hand for 5 minutes. Next, the mixture is centrifuged at 2000 rpm for 10 minutes, and after standing, the aqueous phase component is sucked out from the lower layer with a Pasteur pipette. The phosphorus content of the sucked water phase is measured with an ICP measuring device [ICP-AES manufactured by VARIAN Co., Ltd.].
<Method for measuring isocyanate group content>
The isocyanate group content is measured according to JIS K 7301.
<Measurement method of viscosity>
The viscosity is measured in accordance with JIS K 7117-1.

<Production of Resin Film (F) for Two-Component Curability Confirmation>
The obtained main agent (M) and curing agent (H) were mixed for 5 minutes at 50 revolutions / minute in the number of parts shown in Table 1, and after casting on a glass plate to a thickness of 1 mm, at room temperature for 17 hours, It left still at 80 degreeC for 5 hours, and obtained the resin film (F). Similarly, a comparative resin film was obtained.

<Evaluation of Resin Film (F) for Confirming Two-Component Curability>
The stickiness of the surface of the obtained resin film (F) was sensory evaluated according to the following evaluation criteria.
○: No sticky feeling △: No sticky feeling ×: Sticky feeling

In the two-component curable coating waterproofing material of the present invention, it is preferable that the main agent and the curing agent are uniformly mixed from the viewpoint of molding failure. The curing agent is a diol component, and the main agent that is a urethane prepolymer has a higher viscosity than the diol component. For this reason, the smaller the difference in viscosity between the main agent and the curing agent, the easier it is to mix the main agent and the curing agent, and the molding failure of the coating film hardly occurs.
The molding failure of the coating film can be evaluated by the stickiness of the surface of the resin film (F) obtained from the main agent (M) and the curing agent (H).
As shown in Table 2, in particular, the viscosity difference between the main agent and the curing agent in Examples 37 to 42 is small, and in Example 43 where the water content is slightly large, the viscosity difference between the main agent and the curing agent is slightly large. For this reason, in Examples 37-42, there was no stickiness, and in Example 43, a slightly sticky feeling was felt compared with Examples 37-42. Further, in Example 44, the amount of the phosphate group-containing compound (Q) added was slightly larger than in Examples 37-42, and the urethanization reaction rate was slightly slower. In Example 44, slightly sticky feeling compared to Examples 37-42. Was felt.

  The urethane prepolymer and polyurethane resin using the polyether polyol composition obtained by the production method of the present invention are paints, inks, coating agents, adhesives, sealing materials, waterproofing materials, urethane foams, heat insulating materials, artificial leather, synthetic leathers. It is suitably used for a wide range of applications such as leather, textile products, textile processing agents and automobile parts.

Claims (14)

A polyether polyol composition containing a polyol (a1) having a poly (oxyalkylene) chain, having a water content of 2000 ppm or less, and a phosphate group-containing compound (Q) content of 0.5 to 20 ppm. (A). The polyol (a1) having a poly (oxyalkylene) chain is a diol (a2) having a poly (oxyalkylene) chain, the water content is 300 ppm or less, and the content of the phosphate group-containing compound is 1 to The polyether polyol composition (A) according to claim 1, which is 5 ppm. The polyol (a1) having a poly (oxyalkylene) chain is a diol (a2) having a poly (oxyalkylene) chain, and the polyol (a1) has a hydroxyl value of 28 to 56. A polyether polyol composition (A). The polyether polyol composition (A) according to claim 2 or 3, wherein the diol (a2) having a poly (oxyalkylene) chain is an alkylene oxide adduct of a dihydric alcohol (b1) having 2 to 6 carbon atoms. . The polyether polyol composition (A) according to any one of claims 2 to 4, which is a main component (M0) for a two-component curable coating film waterproofing material. An isocyanate group-terminated urethane prepolymer (P) obtained by reacting the polyether polyol composition (A) according to any one of claims 1 to 5 with an organic polyisocyanate (C). An isocyanate group-terminated urethane prepolymer (P) obtained by reacting the polyether polyol composition (A) according to any one of claims 2 to 5 with an organic polyisocyanate (C). The urethane prepolymer (P) according to claim 7, which is a main component (M) for a two-component curable coating film waterproofing material. Curing containing a main component (M) for a two-component curable coating film waterproofing material which is the isocyanate group-terminated urethane prepolymer (P) according to claim 7 or 8, and a polyol (a1) having a poly (oxyalkylene) chain. A two-component curable coating waterproofing material comprising an agent (H). A polyurethane resin (U) obtained by reacting an active hydrogen component (G) containing the polyether polyol composition (A) according to any one of claims 1 to 5 with an organic polyisocyanate (C). After removing the alkali catalyst from the crude polyether polyol obtained by reacting the alkylene oxide having 2 to 12 carbon atoms with the polyol (a0) in the presence of an alkali catalyst using an adsorbent, dehydrated to obtain a purified polyether polyol. The manufacturing method of the polyether polyol composition (A) which has the process 1 and the process 2 which mixes a phosphoric acid group containing compound (Q) after the said process 1. FIG. The polyhydride according to claim 11, wherein the polyether polyol composition (A) has a water content of 2000 ppm or less, and the phosphate group-containing compound (Q) has a content of 0.5 to 20 ppm. The manufacturing method of an ether polyol composition (A). The isocyanate group terminal which has the process of making the polyether polyol composition (A) and organic polyisocyanate (C) obtained by the manufacturing method of Claim 11 or 12 react, and obtaining an isocyanate group terminal urethane prepolymer (P) Production method of urethane prepolymer (P). The polyether polyol composition (A) is a polyether diol composition (A1), the water content of the polyether polyol composition (A1) is 300 ppm or less, and the polyether polyol composition (A1) The content of the phosphoric acid group-containing compound (Q) is 1 to 5 ppm, and the isocyanate group-terminated urethane prepolymer (P) is a main component (M) for a two-component curable coating film waterproof material. Manufacturing method of isocyanate group terminal urethane prepolymer (P).