TW201139486A - Polyoxyalkylenealcohol and polyurethane resin, and a coating agent containing such polyoxyalkylenealcohol and polyurethane resin - Google Patents

Abstract

This invention provides a novel polyoxy-alkylenealcohol represented by general formula (1). This invention also provides a novel polyurethane resin using this polyoxyalkylenealcohol as a raw material, an aqueous polyurethane resin dispersion in which such a polyurethane resin is dispersed in an aqueous medium, and a coating agent containing such an aqueous polyurethane resin dispersion. Furthermore, this invention further provides an aqueous polyurethane resin dispersion in which the content of a volatile organic compound (a VOC substance) is reduced, and an aqueous polyurethane resin dispersion which can also be dispersed in a mixed solvent containing an ester carbonate which is a non-VOC substance and water.

Description

201139486 VI. Description of the Invention: [Technical Field of the Invention] The present invention provides a novel (tetra) polyoxygenated wire which can form an amine acid vinegar bond with an isocyanate compound, and the polyoxyl extension 6 face is of the general formula (1) indicates. The present invention also provides the use of the novel polylysate lysate prepared by using the polyoxyl extension-tank, which is an aqueous poly-lysal dispersion dispersed in an aqueous medium, and contains W-amine A coating agent for a dispersion of a vinegar resin. Further, the present invention relates to an aqueous polyurethane vinegar resin dispersion which reduces the content of a volatile organic compound (VOOC), and is also dispersible in a mixed solvent of carbon and water containing a non-physical substance. Aqueous polyurethane foam dispersion. [Prior Art] Polyamine-based resin obtained by reaction of a polyol with an isocyanate compound is used for prayer molding, foam H adhesive 'synthetic leather, pigment binder, etc. A useful compound. In addition to being used for the formation of a town or a foam acid, it is usually used as an organic solvent-based polyurethane resin using an organic solvent. In recent years, from the viewpoint of environmental load, the amount of use of the organic solvent has been reduced, and the organic solvent-based polyamine vinegar resin using an organic solvent as a solvent has been converted into an aqueous polyamine using water as a dispersion medium. Vinegar resin is in progress. The aqueous polyurethane vinegar resin is generally a method in which a polyamine acid S resin is mechanically emulsified in water using an external emulsifier, and a hydrophilic group is introduced into the polymer skeleton to be mechanically dispersed in water. 322827 4 201139486 - Yes. An aqueous polyurethane resin in which a hydrophilic group is introduced into a polymer skeleton is known to introduce a hydrophilic group (1) into a carboxylate skeleton, and form an ion pair with a tertiary amine or the like in water. Dispersed anionic aqueous polyurethane vinegar resin '(2) a cationic polyurethane resin which introduces a tertiary amine into an amine ester skeleton and forms an ion pair with an acid component and can be dispersed in water, (3) A nonionic polyurethane resin in which a hydrophilic polyether segment such as polyethylene glycol is introduced into the amine ester main chain in a suspended state to be dispersed in water (see Non-Patent Document 1). Among them, in the case of a nonionic polyurethane resin, a hydrophilic polyalkylene oxide (X-hydrophilic alkylene oxide) is often used. Specifically, proposals for materials (refer to Patent Documents 丨 to 3). Further, in the case of a polyoxyalkylene oxide (p〇ly〇Xyalkylene〇xide), a polybasic oxide formed by stretching an ethyl oxide or a propyl oxide has been reacted with ammonia. (IV) of a polyoxyalkylene alcohol having an amine group (10) 2 group) (Patent Document 4). Further, the organic solvent is carried out in an organic solvent in the production step of the aqueous amino acid brewing resin dispersion. This is due to the addition of an organic solvent and the synthesis of the amine ester prepolymer, mostly

322827 5 The amount of V0C substance of 201139486 (refer to Patent Document 5). [Patent Document] [Patent Document 1] Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 4] Japanese Unexamined Patent Publication No. Hei No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 10-183060. [Non-Patent Document] [Non-Patent Document 1] Development and Application of Aqueous Coating Materials (CMC Publishing, 58 [Problem to be Solved by the Invention] As described above, the polyoxyalkylene alcohol is a raw material which can be used as an aqueous polyurethane resin, but the polyoxyalkylene alcohol of Patent Document 4 is reacted with a polyisocyanate compound. Because of the violent reaction between the amine group and the isocyanate group, the reaction of the polyamine ester resin is difficult to control, and only a hard polyurea resin can be obtained, and a novel one which can form an amine ester bond with the isocyanate compound is desired. Polyoxyalkylene alcohol. Further, for the aqueous polyurethane resin, a product which reduces the amount of the VOC substance in the product is also desired. An object of the present invention is to provide a novel polyoxyalkylene alcohol which can form an amine ester bond with an isocyanate compound, and a novel polyurethane resin using the polyoxyalkylene alcohol as a raw material, the polyamine An aqueous polyurethane resin dispersion in which an acid ester resin is dispersed in an aqueous medium, and a coating agent containing the aqueous polyamine 6 322827 201139486 acid ester resin dispersion. Further, an object of the present invention is to provide an aqueous polyurethane resin dispersion which reduces the content of a volatile organic compound (v〇c substance), and also provides a mixed solvent for a carbonate and water containing a non-VOC substance. Dispersible aqueous polyurethane vinegar resin dispersions are also a subject. [Means for Solving the Problems] The present invention has been made to solve the above problems, and specifically has the following configuration. (1) Polyoxyalkylene alcohol represented by the general formula (1):

~e[(R30)x2/(R40)Y2B-H (1) [〇R5〇)X3/(R60) R7 where R1 to R6 each independently represent a linear or branched carbon number of 2 to 10. Chain-like alkanediyl' These may also contain an alicyclic structure or/and an aromatic ring structure, and R7 represents a linear or branched alkyl group having 1 to 20 carbon atoms, where 'R1 Yin R2, rVr4, r5# R6, X1, X2, Y1, and Y2 indicate that X1+X2+Y1+Y2 is a number of 1 or more and less than 10, and Χ3 and Υ3 each represent a number of 〇 to 135, XI and Y1 'Χ2 and γ2, and 3 And "may be the same or different numbers, both XI and Y1 can be 〇 (zero), 7 322827 201139486 X2 and Y2 are not both 零 (zero), X3 and Y3 are not both 〇 (zero), [] is a block copolymer chain, which may be a random copolymer bond or a homopolymer bond. (2) A polyoxyalkylene alcohol such as (1) has 1 in 1 molecule. An NH2-based amine-based polyalkylene oxide obtained by reacting one or more kinds of extended-base oxides. (3) A polyoxyalkylene alcohol of (2), wherein the alkylene oxide comprises (4) The polyoxyalkylene alcohol of any one of (1) to (3) And the repeating unit of the polyoxyalkylene alcohol has a pendant ethylenoxide unit and/or a propylated oxide unit. (5) The polyoxyalkylene alcohol according to any one of (1) to (4) Wherein at least one of R'O, R20, R30, R40, r5〇, r6〇 is ethylene oxide or propylene oxide. (6) A polyoxyalkylene alcohol as in (5), and At least one of R1〇, r2〇, r3〇, R4〇, R50, and R60 is an ethylene oxide. The polyoxyalkylene alcohol of any one of (1) to (6), The number average molecular weight is from 250 to 6, (8) The polyoxyalkylene alcohol of any one of (1) to (7) having one alkoxy terminal and two hydroxyl groups in its i molecule (9)-polyamine-resin 'system' is at least obtained by reacting polyisophthalic acid vinegar (P〇1yiScK:yanate) with polyoxyl extension alcohol of any of (1) to (8). 322827 8 201139486 ( 10) The polyurethane resin according to (9) is obtained by further reacting with a polyol containing an acidic group. (11) A polyurethane resin such as (10), which is an acid group-containing polyol. The compound is neutralized. (12) The polyurethane of any one of (9) to (11) The resin is obtained by reacting a polyoxyalkylene alcohol with a polyol other than the acid group-containing polyol. (13) The polyurethane resin according to any one of (9) to (12), (14) An aqueous polyurethane resin dispersion obtained by dispersing a polyurethane resin according to any one of (9) to (13) in an aqueous medium. (15) The aqueous polyurethane resin dispersion of (14), wherein the aqueous medium contains carbonate and water. (16) An aqueous polyurethane resin dispersion according to (14) or (15), wherein the carbonated vinegar is selected from the group consisting of dimethyl carbonate, diethyl carbonate and decyl carbonate. More than one type of carbonate. (Π) A coating agent comprising the aqueous polyurethane resin dispersion according to any one of (14) to 6). (18) A method for producing an aqueous polyurethane resin dispersion, which comprises at least a polyisocyanate and a polyoxygen according to any one of (1) to (8) in an organic solvent containing a carbonate. a step of obtaining a polyamine prepolymer by reacting an alkyl alcohol, optionally an acidic group-containing polyol, and a polyol other than a polyoxyalkylene alcohol and an acid group-containing polyol, and a polyamine acid The step of dispersing the vinegar prepolymer in an aqueous medium, 9 322827 201139486, and the step of reacting the polyurethane prepolymer with a chain extender. (19) A method for producing an aqueous polyurethane resin dispersion according to (18), which comprises the step of distilling off the carbonate-containing organic solvent after the step of reacting the polyurethane prepolymer with the chain extender . [Effect of the Invention] According to the present invention, a novel polyoxyalkylene alcohol which can form an amine ester bond with an isocyanate compound, and a novel polyurethane resin using the polyoxyalkylene alcohol as a raw material can be provided. An aqueous polyurethane resin dispersion in which a polyurethane resin is dispersed in an aqueous medium, and a coating agent containing the aqueous polyurethane resin dispersion. Further, according to the present invention, it is possible to provide an aqueous polyurethane resin dispersion which reduces the content of a volatile organic compound (VOOC), and is also long: it can be dispersed for a mixed solvent of a carbonate containing water and a water containing a non-voc substance. Aqueous polyurethane resin dispersion. [Embodiment] [Polyoxyalkylene alcohol (A)] The present invention relates to a polyoxyalkylene alcohol (A) represented by the general formula (1). The polyoxyalkylene alcohol (A) has an alkoxy terminal and one or two hydroxyl terminals in one molecule.

C(R1〇)xi/(R20)yiH-H ΐ(R3〇)x2/ (R4〇)y2}3~H (1) UR5〇)X3/(ReO)Y3B-R7 to R6 each independently represent carbon 2 to 10 linear or branched 322827 10 201139486 alkanediyl groups, these may contain an alicyclic structure or/and an aromatic ring structure, and R7 represents a linear or branched alkyl group having 1 to 20 carbon atoms. Here, RW, RW, XI, X2, Y1, and Y2 indicate that X1+X2+Y1+Y2 is a number of 1 or more and less than 10, and X3 and Y3 each represent a number of 0 to 135, XI and Yl, X2 and Y2, and X3 and Y3 may be the same or different numbers, both XI and Y1 may be 0 (zero), X2 and Y2 are not both 0 (zero), and both X3 and Y3 are not 0 ( Zero), [] is a block copolymer chain, or a random copolymer chain, or a homopolymer chain. In the general formula (1), R1. R20, R30, R40, R50, and R60 each represent a stretch-based oxide unit. Further, in (Ri〇)xl, (R20)Y1, (R30)x2, (R40)Y2, (R50)X3, and (R60)Y3, when XI to X3 and Y1 to Y3 are 2 or more, It is the formation of a polyalkylene oxide. [([^^/(ίΛ);^] may be a random copolymer chain of fo and r2o, or a block copolymer chain, but when either of XI or Y1 is 0 (zero), it means homopolymerization. When the chain of the compound, XI or Y1 is 0, it indicates that a hydrogen atom (H) is bonded to the nitrogen atom (N). [(R30)X2/(R40)Y2] may be a random copolymer of R30 and R40. The chain may also be a block copolymer chain, but when either of X2 or Y2 is 0 (zero), 11 322827 201139486 represents a homopolymer slit. [(R50)x3/(R60)y3] may be r5〇 The random copolymer chain of R6〇 may also be a block copolymer chain, but when either of χ3 or Υ3 is 〇(zero), it represents a homopolymer bond. In the general formula (1), it is bonded to nitrogen. The following general formula (2) of the atom (N) is a part in which, when either one of XI or Y1 is not 〇 (zero), the oxygen atom (〇) having a terminal alkylene oxide unit has a hydrogen atom (H). The bond forms a hydroxyl group at the end. Further, when both XI and Π are 〇 (zero), it means that the moiety represented by the following general formula (2) is a hydrogen atom. -E[(RlO)xi/ (r2〇) h]9—Η (2) In the general formula (1), bonded to a nitrogen atom The general formula (3) indicates that both of Χ2 or Υ2 are not 〇(zero), indicating that the oxygen atom (〇) of the alkylene oxide unit has a hydrogen atom (smart bond). The terminal forms a hydroxyl group. i[(R3〇)X2/(R40)y2B~H (3) In the general formula (1), the moiety represented by the following general formula bonded to the nitrogen atom is either X3 or Y3 Not all 〇 (zero), indicating that the oxygen atom (〇) of the extended-burning oxide unit has an R7 bond of a straight-bonded or branched-chain alkyl group having a carbon number of i to 2 Å, and an alkoxy group is formed at the terminal. —6[(R5〇)x3/(R6〇)Y3]3-R7 (4) In the general formula (1), XI, X2, Y1, and Y2 mean that χι+χ2+γι+γ2 is 1 or more and is not reached. The number of 10. When the sum of X Χ 2 and γ 丫 丫 2 is too large, the content of the aggregate structure on the main chain of the polyacetic acid vinegar is large, and the weather resistance of the polyamic acid vinegar resin is lowered, and the oxygen extension is increased. The use of the burnt base (4) has been limited by the trend of 322827 12 201139486. • In the general formula, X3 and γ3 each represent 0 to 135 bran's ideally each of 0 to 80. \3 and Υ3 Both sides are not all 零 (zero), Χ3 value and Υ3 The total value of the values is desirably 8 to 16 Å. When the total value is too large, the molecular weight of the polyoxyalkylene chain of the nonionic component is too large, and the polyoxyalkylene alcohol (Α) in the present invention is used as When the raw material of the aqueous polyurethane resin dispersion is used, the water repellency of the coating film obtained from the aqueous polyurethane resin dispersion tends to be poor. Further, in order to fix the content of the nonionic component, the polyoxyalkylene is reduced. When the amount of the base alcohol (Α) is increased, the number of polyoxyalkylene groups which are suspended from the main chain of the amine acid ester is small, and the dispersion stability of the prepolymer or the polyurethane resin in the aqueous medium may be deteriorated. Case. The total value is ideally more than 8 160, and more preferably 1 〇 to 12 〇. In the general formula (1), R1 to R6 each independently represent a linear or branched alkanediyl group having 2 to 10 carbon atoms, and these may contain an alicyclic structure or an aromatic ring structure. The linear or branched alkanediyl group having 2 to 10 carbon atoms may, for example, be an ethyl group (-CM:H2-) or a propyl group (-CH(CH3)CH2-). The linear or branched alkanediyl group having 2 to 10 carbon atoms may have an alicyclic structure or/and an aromatic ring structure. At this time, the alicyclic structure or/and the aromatic ring structure may be present on the branch or may be present in such a manner as to interrupt the calcination. The alicyclic structure may, for example, be a cycloalkane residue having 3 to 10 carbon atoms, and examples thereof include a cyclobutane residue, a cyclopentane residue, a bicycloheptane residue, and an adamantine residue. The aromatic ring structure may, for example, be a benzene ring structure or a naphthalene ring structure. These rings may be unsubstituted or substituted for a C 1 to 4 alkyl group 13 322827 201139486. In the general formula (丨), due to the increase in the reactivity of the hydroxyl group of the polyoxyalkylene alcohol (A), R η 3 Λ 〇 〇 and R 〇 are the propyl oxide chain CH. The oxide chain version is chd. In particular, 疋X1 and X2 are 〇(zero), and Y1 and Y2 are 1-3. Furthermore, 'X1 and X2 are 0 (zero), and Y1 and Y2 are ideal. In the general oxime (R), R represents a linear or branched alkyl group having 1 to 20 carbon atoms. The polyoxyxanthene alcohol (4) in the present invention is a hydrogen having at least two 'slot hydrogens ((tetra) hydrogen or/and an amine group) which react with an isocyanate group, and can form an amine acid with an isocyanate compound. Ester bond. The number average molecular weight of the polyoxyalkylene alcohol (A) in the present month is preferably from 250 to 6'. If it is within this range, the obtained polyoxyalkylene group, (A) has a sufficient amount of money, and (iv) a good & good viscosity. The number average molecular weight is more preferably from 400 to 4,000, and _ to 2,500 is particularly desirable. In the present specification, the 'number average molecular weight' means a value calculated from a base price and/or an amine price. The polyoxyalkylene alcohol (A) in the present invention, for example, has an amine group at the terminal, and can be an alkyl group (al) which is an amine group which is mainly composed of a polyalkylene oxide. One or a plurality of kinds of alkylene oxides (a2) are added and reacted. H2 N~f[(R50)x3/(Re〇)Y3]^-R7 (al) where 'only 5, 1^, 1? 7, fork 3 and 丫3 are synonymous with the general formula (1). 322827 14 201139486

In the formula, R8 and R9 are each independently a hydrogen atom, or a linear or branched aliphatic hydrocarbon group or/and an aryl group having 1 to 8 carbon atoms, and R8 and R9 may form an alicyclic structure. The amine-based polyalkylene oxide (al) forms a polyalkylene oxide chain-forming alkylene oxide unit, which can be extended by an ethyl oxide unit, a propylated oxide unit, or a butyl oxide. Object unit, etc. Among them, an ethylidene oxide unit or a propyloxy group unit which can form an alkylene oxide chain having a high hydrophilicity is preferred. In particular, it is preferred that the polyalkylene oxide chain is an amine-based alkylene oxide (al) which is obtained by random copolymerization or block copolymerization of an ethylidene oxide and a propylidene oxide. Furthermore, the poly-extrusion oxide bond is an amine-based polyalkylene oxide (al) which is formed by copolymerization of a pendant ethyl oxide and a propyl oxide. The desired poly-alkyl oxide chain is An amine-based polyalkylene oxide (al) formed by polyethylene oxide is also desirable. In the amine-based polyalkylene oxide (al), the pendant alkyl oxide unit other than the ethylene oxide unit is ideally less than 83 mol% in the total alkylene oxide unit, less than 60 Mol% is more ideal, and less than 25 mol% is particularly desirable. In the amine-based polyalkylene oxide (al), when the ratio of the alkylene oxide unit other than the ethylidene oxide unit in the alkyl oxide unit is increased, the hydrophilicity of the obtained polyoxyalkylene alcohol There is a tendency for the property to decrease, and the use of a polyol which is not suitable as a hydrophilic polyurethane resin such as an aqueous polyurethane resin dispersion has a tendency to be limited. 15 322827 201139486 When the polyoxyalkylene alcohol (A) of the present invention is used as a raw material of an aqueous polyurethane resin dispersion, in the amine-based polyalkylene oxide (al), ethyl epoxide is extended. The alkylene oxide unit other than the material unit is preferably less than 83 mol% in the total alkylene oxide unit, and is preferably less than 60 mol%, and less than 25 mol%. Especially ideal. The end of one side of the aminopolyalkylene oxide (al) is an amine group. The other end is a linear or branched alkyl group having 1 to 20 carbon atoms, and is reactive with alkylene oxide (aikyiene〇xide, the English name and the name of the alkyl oxide) (a2) low. In the case of an aminopolyalkylene oxide (al), a hydroxyl group of a polyether alcohol in which a tertiary ethyl or a propyl oxide is added and polymerized in a tertiary butanol may be substituted with ammonia or the like. In the method of an amine group, a method in which a hydroxyl group of a polyether alcohol to which an alkylene oxide or a propyl oxide is added and polymerized is substituted with an amine to an amine group is used (for example, Japanese Patent Laid-Open No. Hei No. 3-118148 Bulletin) A compound obtained by a known method. Further, in the case of the amine-based compound oxide (al), commercially available products can also be used. For example, JEFFAMINE in which the ratio of the propyl group unit (p0) to the pendant ethyl oxide unit (E0) in the polyalkylene oxide chain sold by the company huntsman is P〇/e〇=9/1 (registered trademark) M-600 (number average molecular weight: 600), or JEFFAMINE (registered trademark) M-1000 (number average molecular weight: 1 〇〇〇) of P〇/E〇=3/19, or p〇/E EFF=29/6 JEFFAMINE (registered trademark) M-2005 (number average molecular weight: 2〇〇〇), or P0/E0=10/31 JEFFAMINE (registered trademark) M_2〇7〇 (number average molecule 322827 201139486 quantity :2000), or Surf® namine B 2〇〇 (number average molecular weight: 2000) of p〇/E〇=95/5. In the above-mentioned commercially available amine-based polyalkylene oxide (al), a polyhydric alkylene alcohol having a relatively high hydrophilicity is obtained by this, and JEFFAMINE (s main registered trademark) M-iooo or JEFFAMINE ( Registered trademark) M 2〇7〇 is ideal. The amine-based polyalkylene oxide (al) has one grade 1 amine, and the average number of knives is preferably from 250 to 6,000, from 4 to 4, more preferably, from 500 to 2,500. Especially ideal. When the number average molecular weight of the amine-based polyalkylene oxide (ai) is too small, the hydrophilicity of the obtained polyoxyalkylene alcohol (A) tends to be small, and when the number average molecular weight is too large, the obtained polyoxyalkylene alcohol ( A) The viscosity is too high and there is a tendency for poor handling. The amine-based polyalkylene oxide (al) is ideal as a compound having more than 4 extended ethylenoxide units as an amine-based alkylene oxide (al) alkylene oxide unit. . The amine-based polyalkylene oxide (al) is preferably an active hydrogen which does not react with an isocyanate group other than the active hydrogen of the amine group. (Alkylene oxide (a2)) is a linear or A branched aliphatic hydrocarbon group or/and an aryl group, and R8 and R9 may also form an alicyclic structure. The linear or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms may, for example, be a linear or branched alkyl group having 1 to 8 carbon atoms, and examples thereof include a mercapto group and an ethyl group. The aryl group may, for example, be a phenyl group or a naphthyl group. ! ^The fat formed by R9 322827 17 201139486 The ring structure can be a ring-fired structure or the like. For the epoxy-fired U2), for example, epoxy bake, epoxy propylene, epoxy T material, or cyelohexene Qxide (tetra) ring type can be suitably used. Epoxy compound. The reaction of the amine-based polyalkylene oxide (al) with the epoxy burn (a2) is a mole of the amine-based polyalkylene oxide (10), which is i mole to 6 moles. It is desirable to carry out the addition of 2 moles to 4 moles (4) of epoxy (10) by mixing, and it is possible to obtain an epoxy-based (a2) addition polymerization polymerization in the amine-based polyalkylene oxide (5). Oxygen extended alcohol. Reaction temperature of amine-based polyalkylene oxide (al) and alkylene oxide (a2)

疋-30C to 400C, ideally 〇c to 350. 〇, more preferably 25 〇C to 30 (TC. In the reaction of the amine-based poly-based oxide (al) and the epoxy-fired (a2), the solvent may or may not be used. Benzene or methylene chloride, etc. The reaction of the amine-based polyalkylene oxide (al) with the alkylene oxide (a2) may be carried out using a catalyst or without using a catalyst. When a catalyst is used, the catalyst is used. In other words, it can be used as a catalyst for sodium hydroxide, hydroxide, sodium carbonate, and carbonic acid. The amount of catalyst added is for the amine-based polyalkylene oxide (al) and alkylene oxide (a2). The total amount is from 1 ppm to 5.0% by weight, desirably from 5 ppm to 1.0% by weight. However, when the polyoxyalkylene alcohol of the present invention is used as a raw material of the aqueous amine ester resin dispersion, From the point of the removal step without the catalyst, it is desirable to carry out the reaction of the amine-based polyalkylene oxide (al) 18 322827 201139486 with alkylene oxide (a2) without using a catalyst. The reaction pressure at the time of reaction of the alkyl oxide (al) with the alkylene oxide (a2) is not particularly specified 'but the alkylene oxide (a2) to be added is prevented from being It is desirable to carry out the reaction under the pressure condition. The alkylene oxide (a2) can be charged into the reaction vessel together with the amine-based polyalkylene oxide (ai), or it can be pre-treated. After the amine-based poly-based oxide (al) is charged, the alkylene oxide (a2) is added dropwise or in portions. The reaction of the amine-based polyalkylene oxide (al) with the alkylene oxide (a2) is carried out. In the case of using an inert catalyst, it is preferable to remove the residual organic catalyst after the reaction is completed. The method for removing the test catalyst may be added with an acid such as phosphoric acid added thereto. And the method of removing the basic catalyst by gradually passing the reaction liquid through the cation exchange resin. Further, in order to remove residual moisture of the reaction system and unreacted alkylene oxide (a2), for example, 13 (rc, h 〇 kPa, dehydration 〇. 5 to 2 hours is ideal. [Polyurate resin] The polyurethane resin of the present invention is at least polyisocyanate (1)) and the above poly The oxygen alkyl alcohol (A) is obtained by a reaction. The method for producing the polyurethane resin is not limited, and all the raw materials may be mentioned. a pre-polymerization method for reacting with a chain extender after reacting a polyoxyalkylene alcohol (A) with a polyisocyanate (D) to produce a prepolymer, from a polyurethane resin The molecular weight of the chick is easy to view ±, ideal for prepolymer methods. Polyurethane resin can be made into various types, for example, in aqueous media 322827 19 201139486 dispersed aqueous polyurethane dispersion, amine ester Foam, thermoplastic polyurethane resin, polyurethane resin solution dispersed or dissolved in an organic solvent, etc. (polyisocyanate (D)) The polyisocyanate (D) in the present invention is as long as 1 molecule The polyisocyanate of two or more isocyanato groups is not particularly limited. Specifically, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-anthracene phenyl diisocyanate (1: 〇1716116 (1^5〇〇乂& 11316, butyl 01), 2,6-methylphenylene diisocyanate, 4,4'-diphenylene diisocyanate (MDI), 2,4-diphenyldecane diisocyanate, 4,4' -diisocyanatobiphenyl, 3,3'-dimercapto-4,4'-diisocyanatobiphenyl, 3,3'-dimercapto-4,4'-diisocyanato Diphenyldecane, 1,5-anaphthyl diisocyanate, 4, 4',4"-triphenyldecane triisocyanate, m-isocyanatophenylsulfonyl isocyanate, p-isocyanate Alkyl phenylsulfonyl isocyanate, an aromatic polyisocyanate compound such as phenyl bis(isopropyl isocyanate) (TMXDI); ethyl diisocyanate, tetramethylene diisocyanate, hexamethylene dicyanate HDI), dodecyl decyl diisocyanate, 1,6, 11-undecyl triisocyanate, 2, 2, 4-tridecyl hexamethylene diisocyanate, diazonic acid diisocyanate, 2, 6- Diisocyanatodecyl hexanoate, bis(2-isocyanato) An aliphatic polyisocyanate compound such as ethyl)fumarate, bis(2-isocyanatoethyl)carbonate or 2-isocyanatoethyl-2,6-diisocyanatohexanoate; Isophorone diisocyanate (IPDI), 4,4'-di cyclohexyl methane di isocyanate (hydrogenated MDI), 20 322827 201139486 Cyclohexyl Cyclohexylene diisocyanate, methylcyclohexyl diisocyanate (argonized TDI), bis(2-isocyanatoethyl)-4-cyclohexyl-1,2-dicarboxylate, 2, 5- An alicyclic polyisocyanate compound such as a decane diisocyanate or a 2, 6-anthracene diisocyanate may be used alone or in combination of two or more. The isocyanate group in one molecule of the isocyanate is usually two, but in the range where the polyurethane resin in the present invention is not gelled, three such as triphenyldecane tricyanate may be used. The above polyisocyanate isocyanate. In the polyisocyanate, from the viewpoint of the regulation of reactivity, isophorone diisocyanate Ester (IPDI) '4, 4'-dicyclohexyldecane diisocyanate (hydrogenated MDI), phenyl bis(isopropyl isocyanate) (TMXDI) is preferred. In the manufacture of the polyurethane resin of the present invention Further, a polyol (B) containing an acidic group, and a polyhydric alcohol (A) and a polyol other than the acidic group-containing polyol (B) (hereinafter referred to as "other polyols") may be used in combination. (Polymer group-containing polyol (B)) The acid group-containing polyol (B) in the present invention contains an acidic group having two or more hydroxyl groups and one or more acidic groups in one molecule. The polyol is not particularly limited. The acidic group may be a functional group having a Bronsted acid function such as a carboxyl group or a fluorenyl group. The acidic group may be a hydrazine acid group or a phenolic hydroxy group. Specific examples thereof include dihydroxymethyl alkanolic acid such as 2,2-dimethylolpropionic acid and 2,2-dihydroxydecylbutyric acid; hydrazine, hydrazine-bishydroxyethylglycine; — bishydroxyethyl alanine ' 3, 4-dihydroxybutanesulfonic acid, 3, 6-dihydroxy-2-indolene benzenesulfonic acid, and the like. 21 322827 201139486. It is also possible to use these two kinds of diols containing a base. Among the polyhydric alcohols having a severe group, it is desirable to use 2'2_-anthracene group called '2H-decyl tauric acid from the viewpoint of easy starting. (Other polyols) The other polyol (6) in the present invention is not particularly limited as long as it is a polyol compound other than the base alcohol (A) and the acidic group-containing polyol (8), and for example, it can be used. A number average molecular weight _ to 5' of a polymer polyol ((1) and/or a low knife kiln alcohol having a number average molecular weight of less than 400 ((2), etc. especially 'the aforementioned high molecular weight polyol (C1) with low molecular weight The polyol (C2) is preferably used in combination. When the high molecular weight poly(tetra) ((1) and the low molecular weight polyol (10) are used in combination, the ratio of the polymer polyol in the total amount of the other polyols (C) is not particularly Preferably, the polymer polyol (C1) is preferably from 8 G to 99% by weight, preferably from 90 to 98% by weight. The high molecular weight polyol (C1) may, for example, be a polycarbonate diol. Polycarboxylate diol, polycarbonate ether diol, polyester diol, polyester ether diol and polyether diol, etc. The point of adhesion and &, by polychloric acid® sterol, poly stone acid The diol is preferably one or more selected from the group consisting of polyglycol diols. The polycarbonate monool is not particularly limited, and a compound obtainable by a usual production method can be used. Specifically, a diol compound can be used. (ethylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 16-hexanediol, 18_322827 22 201139486 octanediol, decanediol, 1,10-癸2 Alcohol, 1,12-dodecanediol, 1,4-cyclohexanediol, etc. These may be used alone or in combination of two or more kinds thereof with dimethyl carbonate, diethyl carbonate or carbonic acid. a compound obtained by reacting a carbonate compound such as ethyl ester and deolating the compound; a compound obtained by a method of transesterifying the diol compound with a diaryl carbonate (for example, diphenyl carbonate), etc. The alcohol is, for example, a polycarbonate diol having a linear alkyl group having 4 to 12 carbon atoms (for example, polytetramethylene carbonate diol, polypentamethylene carbonate diol, Polyhexamethylene carbonate diol, polycarbonate diol of decanediol, polycarbonate of decanediol, polycarbonate of dodecanediol a polycarbonate diol having a branched alkyl group having 4 to 12 carbon atoms (for example, a polycarbonate diol of 2-mercaptobutane diol, a polycarbonate of 2-ethylbutane diol) a diol, a polycarbonate diol of neopentyl glycol, a polycarbonate diol of 2-mercapto diol, a polycarboxylate diol of 3-methyl pentane diol, etc.; and a copolymer of these The polyester diol is not particularly limited, and a compound obtainable by a usual production method can be used. Specifically, a diol compound (the same compound as described above) and a dicarboxylic acid compound (aliphatic compound) can be used. Carboxylic acid (succinic acid, adipic acid, hydrazine monoacid, hydrazine monoacid, dodecanoic acid, dimeric acid, etc.), aromatic monoacid (for terephthalic acid) , isophthalic acid, phthalic acid, etc. These may be used singly or in combination of two or more kinds of compounds (reaction); lactones (ε-caprolactone, γ-butyrolactone, Τ-valerolactone, etc. These may be used alone. A compound which can be obtained by ring-opening polymerization of 2 23 322827 201139486 or more may be used in combination. The polytrimethylene glycol is not particularly limited, and an α-α which can be used in a usual production method can be used. Specifically, an alkyl ene oxide (extended ethyl oxide, propyl oxide, 1, 2, 2, 3) may be mentioned as a diol compound (the same compound as described above). -, or 1,3-butyl butyl oxide, tetrahydroanthracene, ethylene oxide, alpha-olefin oxide, epichlorhydrin, etc. These can be used alone 1 a kind of 'addition of two or more kinds of addition reactions", without using a catalyst, or in the presence of a catalyst (alkali catalyst, amine catalyst, acid catalyst), under normal pressure or under pressure, 1 section A compound or the like which can be obtained in a plurality of stages. Further, the addition form when two or more kinds of alkylene oxides are used may be a block shape or a random form. The low molecular weight polyol (C2) may, for example, be a polyhydric alcohol having 2 to 15 carbon atoms (a divalent alcohol (for example, ethylene glycol, 1,3-propanediol, 2-methyl-1, 3-propanediol, 2) ,2-dimethyl-i,3-propanediol, 2-butyl- 2-ethyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-hydrazino <5-Pentanediol, 16-hexanediol, alkane (carbon number 7-22) diol, diethylene glycol, triethylene glycol, tetraethylene alcohol 荨月曰 aliphatic diol: 1,4 - cyclohexane dimethanol, cycloheximide dimethanol, 1' 4-cyclohexanediol, 1,4 bis(hydroxyethyl)cyclohexane, 2,7-norbornanediol, tetrahydrofuran dimethanol 2,5_bis (hydroxyl-based oxime dioxane, etc., diol having a condensed ring structure of 6 to 12, etc.); an alcohol having a valence of 3 or more (for example, glycerin, dimethylolpropane, sorbitol) Sugar alcohols, etc.; alkylene oxides (E0 and/or p〇) of these polyols are low molar additions (Mn is less than 4 Å). (Polyurate Prepolymer (E)) 24 322827 201139486 In the method for producing a polyurethane resin of the present invention, when a prepolymer is used, it is passed through a prepolymer prepolymer of a polyurethane ( E). The polyurethane prepolymer (E) is a compound obtained by reacting at least a polyoxyalkylene alcohol (A) with another polyol (C) and a polyisocyanate (D), and an acid group-containing polyol. (B) is an optional component. The polyoxyalkylene alcohol (A), the acidic group-containing polyol (B) with any component, and the other polyol (C) have the molar number of active argon, polyisocyanate (D) The ratio of the number of moles of the cyanate group is from 1.01 to 2. 5 is ideal, and from 1.2 to 2. 2 is more desirable, and from 1.2 to 2.0 is particularly desirable. When the total weight of the polyoxyalkylene alcohol (A) and the acidic group-containing polyol (B) and the other polyol (C) and the polyisocyanate (D) is 100 parts by weight, the acidity is contained. The weight ratio of the polyol (B) is preferably from 0.01 to 30 parts by weight, more preferably from 0.05 to 25 parts by weight, particularly preferably from 0.1 to 15 parts by weight. When the weight fraction of the acid group-containing polyol (B) is too large, the water resistance of the obtained polyurethane resin tends to be poor. When the number of moles of the isocyanate group of the polyisocyanate (D) is too large, such as the molar number of active hydrogen, the viscosity of the obtained polyurethane prepolymer (E) becomes high, stirring or dispersion in an aqueous medium. There are difficult trends. Further, when the number of moles of the isocyanate group is too small, such as the number of moles of active hydrogen, the unreacted polyisocyanate (D) remains in the reaction system in a large amount, and the amount of heat generated in the reaction of the chain extender is increased. Therefore, the regulation of the reaction temperature becomes difficult, and there is a tendency to form a gelatinous polyurethane resin. In the production of a polyurethane resin or a polyurethane prepolymer (E), the molar ratio of the acidic group-containing polyol (B) 25 322827 201139486 when the acid group-containing polyol (B) is used. When the number of moles of the polyoxyalkylene alcohol (A) is small, the acidic group of the acidic group-containing polyol (B) is not neutralized, and the aqueous polyurethane resin dispersion is stably dispersed in the aqueous medium. . That is, the point of the neutralization step can be omitted. 'In the manufacture of the polyurethane resin and the polyurethane prepolymer, the amount of the polyol (B) containing the acidic group is less than that of the polyoxyalkylene alcohol. The number of moles of (A) is less than ideal. When obtaining the polyurethane prepolymer (E), the polyoxyalkylene alcohol (a), the acidic group-containing polyol (B), the other polyol (c), and the polyisocyanate (for any component) In the reaction of D), (A), optional components (b), (c) may be reacted with (D) in a different order, or (A), optional components (B), and (〇) may be mixed. Reaction with (D) The content of polyoxyalkylene alcohol units in the polyurethane prepolymer (E) is preferably from 3 to 60% by weight. In the polyurethane prepolymer When the polyoxyalkylene alcohol unit in (E) is too small, the hydrophilicity of the obtained polyamic acid brewing resin becomes low, or when the aqueous polyurethane resin dispersion is produced using the polyurethane prepolymer, The polyamino acid g is intended to have a difficulty in dispersing the prepolymer (1) in an aqueous medium. The polyoxo-alcohol in the polymer (8) is a polyamine ester tree. The long-term stability of 曰 has a tendency to change (4). The content ratio of polyoxy(tetra)hydrinol units is preferably from 8 to 40%. Further, in the present invention, the term "polyoxyalkylene alcohol" The radicals of the radicals are removed from the hydrogen atom: _. As early as the polyoxyl extension alcohol (A), with any component knife ° alcohol (8) 'other polyols (C)' and multiple heterogeneous jun 2 = can be used Catalyst.) 322827 26 201139486 * Catalyst 疋; there are special restrictions 'But for example: tin-based catalyst (three = base, laurate, dibutyl tin dilaurate, etc.) or lead Catalyst (Xin Yi Wen Jin. Special) and other metals and organic and inorganic acid salts, and organometallic derivatives private 'catalyst (triethylamine, N-ethyl chlorene, triethylenediamine, etc.), dinitrogen Diazabicycloundecene is a catalyst or the like. Among them, dibutyltin dilaurate is preferred from the viewpoint of reactivity. -^Polyoxy-ternyl alcohol (A)' and other components containing an acidic group: alcohol oxime, other polyol (6)' and polyisocyanate vinegar (8) reacted at a temperature of 5, there is no particular limitation , but 40 to 15 〇〇 c is ideal. When the reaction temperature is too low, the raw material is not dissolved, or the viscosity of the obtained polyurethane prepolymer is too high to be sufficiently mixed. Further, when the reaction temperature is too high, there is a case where a side reaction or the like is disadvantageous. The reaction temperature is preferably from (10) to 120 °C. The reaction of the β polyoxyl alcohol (A) ' with an acidic group-containing polyol (8) having an optional component, another polyol (6), and polyisocyanate (4) (9) may be carried out without a solvent or with an organic solvent. The organic "combination medium" & ' is preferably an organic solvent containing a carbonate. Carbon: 曰:. It can use dialkyl carbonate such as sulphuric acid dimethyl vinegar, diacetic acid carbonate, ethylene carbonate acetonitrile, dipropyl carbonate or dibutyl carbonate, and ethyl carbonate: Brewed and other diaryl carbonate, carbonated vinegar, benzene vinegar, carbon, sulphur, sulphur, sulphur, sulphur, sulphur, sulphuric acid, sulphuric acid, sulphuric acid, sulphuric acid, sulphuric acid, sulphuric acid, sulphuric acid At least one or more of ethyl acetonate and ethyl methyl carbonate are more preferred. Organic hydrazine, in addition to carbonate, can also be added to propylene, methyl ethyl 27 322827 201139486 ketone, methyl isobutyl ketone, tetrahydrofuran, two noise, dimethyl decylamine, two曱基亚磨, N-decylpyrrolidone, N-ethylpyrrolidone, ethyl acetate, and the like. Among them, acetone, methyl ethyl ketone, and ethyl acetate are preferably removed from the organic solvent by dispersing the polyamine vinegar. prepolymer in water and chain extension reaction, and then removing it by heating under reduced pressure. Further, N-mercaptopyrrolone or N-ethylpyrrolidone is preferred as a film-forming aid when it is used as a coating film for an aqueous polyurethane resin dispersion. Substitution of a portion of the organic solvent with a carbonate reduces the amount of VOC material in the article. Further, since the substance in the product can be reduced, it is preferable that the organic solvent is only carbonate. The organic solvent is added in an amount of 100 parts by weight of the polyoxyalkylene alcohol (A) and the acidic group-containing polyol (B) of any component, and the other polyols (〇, and the polyisocyanate (D). In the case of a part, it is preferably 3 to 35 parts by weight. The organic solvent may be added to the system when the prepolymer is produced as described above, or may be added before being dispersed in the aqueous medium after the prepolymer is produced. (F)) In the polyurethane resin of the present invention, when the polybasic group containing an acidic group = (B) is used, the acidic group of the polyol (B) containing an acidic group can be neutralized, and it is also found that it is not neutralized. In order to improve the dispersibility of the polyurethane resin to the aqueous medium, it is desirable to neutralize the acidic group with the basic compound (F) and the acid group-containing polyol (b) derived from the polyamine resin. The number of protons in the material reaction, such as the tb polyoxylinol (A), the tertiary amine of the polyoxyalkylene alcohol has the function of neutralizing the acidic group, 322827 28 201139486 Therefore, it is not necessary to use the test compound. (F) is also possible. Using the acidic group of the test compound (F) It can be carried out after reacting the acidic group-containing polyol (B) with the polyoxyalkylene alcohol (a), other polyol (c), and polyisocyanate (D). The aqueous polymer is produced by the prepolymer method. In the case of the amine ester resin dispersion, the basic compound (F) and the polyurethane prepolymer (E) may be previously mixed and redispersed in an aqueous medium. The basic compound (F) may also be premixed with the aqueous medium. Thereafter, the polyurethane prepolymer (E) is dispersed in an aqueous medium, and the polyamine prepolymer (E) may be dispersed in an aqueous medium while the test compound (F) is added to the aqueous medium. The test compound may, for example, be tridecylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, n-styldiethanolamine, dimercaptoethanolamine, diethyl Organic amines such as benzylamine, decylmorpholine, and pyridine; inorganic bases such as sodium hydroxide and potassium hydroxide, ammonia, etc. The above organic amines are preferred, and tertiary amines such as triethylamine are more preferred. (F), derived from the use of acid in the manufacture of polyurethane resin The number of protons in the reaction of the acidic group-based basic substance of the polyol (B) is preferably from the range of 〇 to 3·G times the molar nj, and is more preferably in the range of 倍 to 1.5 times the molar. Chain extender (G)) The chain extender (G) is not particularly limited as long as it is a functional group reactive with an isocyanate group of the polyurethane prepolymer (E). Chain extender (G) For example, ethylenediamine, tetramethylenediamine, 2-methyl-1,5-pentanediamine, h 4 -butylene diamine, 16 6 hexamethylene 曱 322827 29 201139486 Monoamine 1'4, fluorenyldiamine, 3-aminoguanidinotrimethylcyclohexylamine 1,3 bis(aminomethyl)cyclohexane, m-xylylenediamine (light (10) diamine), Material, 2,5' dimethyl material, diethylenetriamine, triethylenetetramine compound 'ethylene glycol, propylene glycol 'butanediol, "_hexanediol-alcohol compound' polyethylene glycol (4) These two kinds of wire can be used alone or in combination of two or more. The amount of addition of the chain extension (4) (G) is 1 equivalent of the isocyanate group at the starting point of the bond extension in the obtained (4) moving prepolymer! The equivalent of the equivalent or less is desirable, and it is more desirable that the equivalent amount of the iso-acid group is from U to 0.99 equivalents. For the different: acid group: when (10) plus more than one equivalent of the chain extender (6) a, the extended chain of the molecule 1 is reduced, the resulting polyamine acid (tetra) lipid or coating: the factory polyamine vinegar resin dispersion obtained by coating The strength of the film has a declining potential. The water-added polyamine _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ At this time, the water of the dispersion medium is a reaction 4 in which the chain amino acid: the chelating compound (8) reacts with the bond extender (8). For example, 〇 to 8 rc is preferable, and more desirably 〇 to _. = hair _ water _ _ gamma dispersion is formed in the water (four) body knife polyurethane resin. ^The secret of the body can be water, and the mixing of water and hydrophilic money solvent: = and so on. For water, tap water 'ion exchange water, steamed water, 4'. The hydrophilic organic solvent may be a low-grade monovalent alcohol such as methanol, ethanol or propanol or a polyhydric alcohol such as ethylene glycol or glycerin, in addition to the organic solvent to be added to the prepolymerized 322827 30 201139486 polyamino acid; An aprotic hydrophilic organic solvent such as N-mercaptomorpholine, dimercaptosulfoxide, dinonylguanamine, N-methylpyrrolidone or N-ethylpyrrolidone. The amount of the hydrophilic organic solvent in the aqueous medium is preferably from 0 to 20% by weight. In the present invention, a mixed medium containing carbonate and water can be used as the permanent medium. Examples of the carbonate include dimethyl carbonate, diethyl carbonate, and ethyl phthalate. In addition to the carbonate and water, the above hydrophilic organic solvent may be added. However, from the viewpoint that the VOC content is small, a mixed medium of carbonate and water is preferable. The ratio of the carbonate in the aqueous medium is preferably from 1 to 15 parts by weight based on 100 parts by weight of the entire aqueous medium. When the content of the carbonate is too large, the product may be separated by a carbonate. (Aqueous Polyurethane Resin Dispersion) In the production of an aqueous polyurethane dispersion, a polyoxyalkylene alcohol (A), an acidic group-containing polyol (B) having an optional component, and other polyols (C), the step of reacting the polycyanate (D) to obtain the polyurethane prepolymer (E), may be carried out in an inert gas atmosphere or in an atmosphere. The step of neutralizing the polyurethane prepolymer (E) with the basic compound (F) can be carried out under an inert gas atmosphere or under an atmospheric environment. The step of reacting the polyurethane prepolymer (E) with the chain extender (G) to obtain an aqueous polyurethane resin can be carried out under an inert gas atmosphere or in an atmosphere. The method of dispersing an aqueous polyurethane resin in an aqueous medium is not limited to the specific one, but it is exemplified by adding a polyurethane in an aqueous medium under stirring using a homomixer or a homogenizer. A method of prepolymer or a polyurethane prepolymer solution, a method of adding an aqueous medium to a stirred polyurethane prepolymer using a homomixer or a homogenizer, or the like. When the polyurethane prepolymer (E) is reacted with a chain extender (G) to obtain an aqueous polyurethane resin, the chain extender (G) can be added under cooling to carry out the reaction 'also at 60 ° C The reaction is promoted under the following heating conditions. The ratio (solid content ratio) of the polyamic acid resin in the aqueous polyurethane resin dispersion of the present invention is desirably 5 to 60% by weight, and more preferably 20 to 50% by weight. The aqueous polyurethane vinegar resin dispersion can be subjected to the aforementioned organic solvent under reduced pressure. The organic solvent can also be carried out under heating or falling. The aqueous polyurethane resin of the present invention can be suitably blended with various additives according to the purpose and use, for example, a plasticizer, a foaming agent, and an antifoaming agent. Leveling agent, anti-fungal agent, anti-rust agent, anti-gloss agent, flame retardant, thixotropic agent, adhesive agent, enriching agent, slip agent, antistatic agent, interface activity Agent, reaction retarder, anti-oxidation agent, ultraviolet absorber, water-repellent agent, weathering stabilizer, dye, inorganic pigment, extender pigment, hardener, folding preventive agent, etc. The blending ratio of these various additives can be appropriately selected depending on the purpose and use. The coating agent of the present invention contains the aqueous polyurethane vinegar resin dispersion of the present invention. If necessary, the above additives may be added. The coating agent of the present invention can be coated on the base 322827 32 201139486 by a known casting method such as a laminate method or a known coating method such as a direct coating method, and the coating method can be used for its purpose and use. And suitable for selection. Further, the aqueous polyurethane resin dispersion of the present invention can be suitably used, for example, in various coating applications such as automobiles, electronic equipment, building materials, and artificial leather. When a carbonate is used as the aqueous medium, the method for producing the aqueous polyurethane resin dispersion of the present invention has at least the following steps. The following steps (τ) and steps ((5) may be carried out sequentially or simultaneously. Among the organic solvents containing carbonate, at least, polyisocyanate (D), and polyoxyalkylene alcohol (A), The step (α) of reacting the acidic group-containing polyol (B) and the other polyol (C), as the case may be, to obtain the polyurethane prepolymer (E); pre-treating the polyurethane in an aqueous medium a step of dispersing a polymer (Ε) (7〇; a step of reacting a polyurethane prepolymer (Ε) with a chain extender (G). It is a raw material of the aqueous polyurethane resin of the present invention. When a polyol having an acidic group is used, when the acidic group is neutralized, the following steps are carried out. The following steps (r) and (5) may be carried out sequentially or simultaneously. In the organic solvent containing a carbonate, at least the polyisocyanate (D) is reacted with the polyoxyalkylene alcohol (A), the acidic group-containing polyol (B), and other polyol (C). Step (α) of the polyurethane prepolymer (E). The acidic group of the polyurethane prepolymer (Ε) is in the basic compound (F) And steps (10,000) 33 322827 201139486 Step (r) of dispersing the polyurethane prepolymer (E) in aqueous media 〇Polyurethane prepolymer (E) and chain extender (G) Step (5). [Examples] Hereinafter, the present invention will be specifically described with reference to the examples and comparative examples, but these are not limited to the present invention. Further, unless otherwise specified, "%" means a weight basis. The measurement of each amine price was carried out by the following method. <Total amine valence> The total amine valence was calculated by titration with a potential difference using a perchloric acid-glacial acetic acid titration solution (0.1 N), a crystallized violet indicator, and an glacial acetic acid solvent. The amount of perchloric acid required is the equivalent number of milligrams of hydroxide. <3 grade amine price> Grade 3 amine valence, using perchloric acid-glacial acetic acid titration solution (0.1 N), crystal violet red (cry 1 sta 1 viο 1 et) indicator, glacial acetic acid and acetic acid needle 1: The capacity of 9 is calculated by potentiometric difference from the mixed solvent, and the amount of perchloric acid required to neutralize the sample lg is calculated as the equivalent amount of potassium hydroxide. <Total amount of grade 2 amine price and grade 3 amine price> In the sample, hydrous acid aldehyde is reacted with the first amine, and hydrochloric acid ethanol titration solution (0.1 N), bromocresol green indicator is used. The amount of hydrochloric acid required to neutralize the sample lg was calculated by potentiometric titration to be the same amount of mg of hydrazine hydroxide. 34 322827 201139486 <Grade 2 amine price> The amine valence of the second grade is the potassium hydroxide per lg sample calculated from the measured value of the total of the amine grade of the second grade and the amine grade of the third grade minus the measured value of the amine grade of the third grade. The number of mg. <1 grade amine price> The grade 1 amine valence is the mg of potassium hydroxide per lg of the sample, which is calculated from the measured value of the total amine valence minus the total value of the quaternary amine valence and the quaternary amine valence. The number 0 hydroxyl number is measured in accordance with the B method of JIS K 1557. Further, the moisture was measured by a water titration method using a Karl Fischer moisture meter. The number average molecular weight is calculated from the hydroxyl value as follows. Number average molecular weight = 112200 / (hydroxyl value of polyoxyalkylene alcohol) The components used in the examples are as follows. • "JEFFAMINE M-1000"··Huntsman Co., Ltd. is a poly(propylene oxide/extension ethyl oxide=3/19 molar ratio) copolymer with a first-stage amine, number average molecular weight 1, 〇 Hey. • "JEFFAMINE M-2070": A poly(propylene oxide/extension ethyl oxide = 10/31 molar ratio) copolymer of the first grade amine, manufactured by Huntsman, having a number average molecular weight of 2,000. • "ETERNACALL UH-200": Polyhexamethylene carbonate with a first-order alcohol at both ends of Ube Industries, Ltd., with an average molecular weight of 2,000 「 • "ETERNACALL UHC50-200": Ube Industries, Ltd. 35 322827 201139486 Polycaprolactone/polyhexamethylene carbonate (1 molar molar ratio) copolymer of a 1st alcohol at both ends, having a number average molecular weight of 2,000. • "Nipporan 4009": Polybutanediol adipate of the first-order alcohol at both ends of URETHEANE, Japan, with a number average molecular weight of 1,000. • “Terathane 2000”: a polytetramethylene glycol produced by Dupont Company with a 1st alcohol at both ends and a number average molecular weight of 2,000. Example 1 (polyoxyalkylene alcohol A1) A stainless steel autoclave equipped with a thermometer, a nitrogen gas introduction tube, an ethylene oxide introduction tube, a temperature adjustment function, and a stirrer was charged with an amine-based polyalkylene oxide oxide. (aminopolyalkylene oxide) (JEFFAMINE M-1000 (peramine equivalent = 1. 00 meq/g, grade 1 amine content: 100%), manufactured by HUNTSMAN) 4000 g (4 mol), after replacement with nitrogen, stirring, 16 (rc The ethylene oxide 361g (8.2 moles) was introduced in batches at a rate of 1 hour. The reaction was completed at 16 (TC) for 3 hours. The obtained reaction solution was at 130. (: state, treatment under reduced pressure of 1 kPa 1 The polyoxyalkylene alcohol A1 is obtained in an hour. The polyoxyalkylene alcohol A1 compound is a colorless transparent liquid in a molten state of 40 C, and has a moisture content of 〇 5%, a hydroxyl value of 93.9 mg K0H/g, and a melting point of 12. 5〇C, freezing point 25. ιχ. From the determination of total amine valence, grade 3 amine valence, grade 2 amine valence, grade 1 amine valence, it is known that the grade III amine content is 97.4% 'the grade 2 amine content is 11%, grade 1 The amine content is 15%. The number average molecular weight of the obtained polyoxyalkylene alcohol is 1〇88, and the amine group of the above-mentioned amine-based polysilicic oxide is obtained, and there is an ethylene compound 2 molecular addition. A polyamine alkyl alcohol of a tertiary amine. 322827 36 201139486 Example 2 (polyoxyalkylene alcohol A2) equipped with a thermometer, a nitrogen introduction tube, an introduction tube for epoxy bromide, a temperature adjustment function, and a mixer In the non-recorded steel high pressure crucible, the amine-based poly-extension base oxide is added (8111丨11〇卩〇1丫811^16 this €^(16)(several??810 service 1^-2070 (full The amine equivalent = 0.48 meq/g, the first grade amine content is 99.3%), 4140 g (2.0 m) manufactured by HUNTSMAN Co., Ltd., after being replaced with nitrogen, it is stirred in an hour, i6 〇 °c for 1 hour. 181 g (4.1 mol) of ethylene oxide was introduced, and the reaction was completed at 16 (TC) for 3 hours. The obtained reaction solution was treated under a reduced pressure of 1 〇kpa for 1 hour in a state of 130 〇c to obtain a polyoxygen extension. The alkyl alcohol A2. The polyoxyalkylene alcohol A2 compound is a colorless transparent liquid at room temperature, moisture 〇. 06%, the base price is 51.7 mg KOH / g, from the full amine valence, the tertiary amine valence, the second amine 0%。 The number average amine content is 96.7%, the amine content of the second grade is 1.3%, the amine content of the first grade is 2.0%. The number average of the obtained polyoxyalkylene alcohol The molecular weight is 2171, which results in the oxidation of the aforementioned amine-based polyalkylene On the amine group, there is a polyoxyalkylene alcohol of a tertiary amine of 2 molecules added with ethylene oxide. Example 3 (aqueous polyurethane resin dispersion-1) equipped with a stirrer, a nitrogen introduction tube, and heating 4,4'-methylene bis(cyclohexylisocyanate) (4,4'-methylene bis(cyclohexylisocyanate) (trade name "Desmodur W", Bayer) in a 4-neck separable flask 5), 6 g, a polycarbonate diol having a number average molecular weight of 2000 as a polyol (trade name "ETERNACOLL UH-200", manufactured by Ube Industries Co., Ltd.) i〇i. 5 g, and the polymerization obtained in Example 1. 66. 0g, N-mercaptopyrrolidone of Oxyalkylene A1 (Mitsubishi Chemical Co., Ltd. 37 322827 201139486. Miscellaneous. Adding Micro-Jin & Lauric Acid as a Reaction Catalyst under Nitrogen (Wako Pure Chemical Company) The system was reacted for 4 hours to obtain a polyamine-counter compound. Polyamine: rate up _ slowly added to keep in the _ mix „ (four) financial H 2 〇〇, dispersion: add 35 to give methyl 丨, 5- pentyl diamine 〇 = make it into Chain extension reaction 'The resulting dispersion was filtered through 120 mesh: 17.8 g to obtain an aqueous polyurethane-resin dispersion + scale steel mesh 93⁄4. The obtained aqueous polyurethane resin dispersion _ 丨 solid viscosity at 耽 is 38 mPa .s., the agricultural degree is 30. During the storage at 40 ° C for 4 months in a sealed state, the separation is not ancient, and the dispersion state is maintained. ♦ To the resin, Example 4 (aqueous polyurethane resin dispersion - 2) In a bottle equipped with a stirrer, a nitrogen inlet pipe and a heater, '4,4, _methylene double-sheet detachable, burnt ester is added to the polyisocyanate vinegar (trade name "DesmodurW", manufactured by Bayer ) 56 i The number of the average molecular weight of the isocyanoid alcohol f 2000 is more than "ETERNACOLL UHC5 〇 2 〇〇" 'made by Ube Industries Co., Ltd.) J, and in Example 1 79. 5g of the obtained polyoxyalkylene alcohol A1, and the ratio of the product to the product (Mitsubishi Chemical Co., Ltd.) 15.Gg' is as a reaction medium under a nitrogen atmosphere. Dibutyl tin dilaurate (Wako Pure Chemical Industries, Ltd.) for 4 hours to give a reaction rate of 99% or more polyamine ester prepolymer. The polyacrylate prepolymer 20.0 g was slowly added to 387 g of distilled water maintained under strong stirring to disperse it, and 35 wt% of a 2-methylq 5:pentanediamine aqueous solution was added. 17. 2g was subjected to a chain extension reaction, and the resulting dispersion was filtered through a stainless steel mesh of 322827 38 201139486 120 mesh to obtain an aqueous polyurethane resin dispersion-2. The solid content concentration of the obtained aqueous polyurethane resin dispersion 2 was 32.%, and the viscosity at 20 ° C was 48 mPa·s. During the storage in the Φ closed state 40 C for 2 months, no separation of the resin component was observed, and the dispersion state was maintained. Example 5 (Aqueous Polyurethane Resin Dispersion_3) A 4-neck separable flask equipped with a mixer, a nitrogen introduction tube and a heater, and a 4,4,--fluorenylene double of polyisocyanate was charged. (cyclohexyl isocyanate) (trade name "Desmodur W", manufactured by Bayer Co., Ltd.) 67. 8 g, polyester diol (manufactured by Nipporan 4009, manufactured by URETHANE, Japan) as a polyhydric alcohol having a number average molecular weight of 1,000. 〇g, and 5.8 g of the polyoxyalkylene alcohol A1 obtained in the example, N-methylpyrrolidone (manufactured by Mitsubishi Chemical Corporation) 18.8 g, and a trace amount of the reaction catalyst was added under a nitrogen atmosphere. Dibutyltin laurate (manufactured by Wako Pure Chemical Industries, Ltd.), reacted at a reaction rate of 99% or more for 4 hours to obtain a polyurethane prepolymer. The polyurethane prepolymer 200 was gradually added to 376 g of distilled water maintained under a strong stirring state to be dispersed, and a solution of 35% by weight of a base solution of 5% by weight of a solution of 25% by weight of a solution The chain extension reaction was carried out, and the obtained dispersion was filtered through a mesh of a mesh of iodine, and the aqueous polyamine acid S was used as a resin dispersion-3. The obtained aqueous polyurethane resin dispersion-3 had a solid content concentration of 32.0% and a viscosity at 20 Torr of 42 mpa.s. In the fee closed state 40. (: During the storage for 2 months, the resin of the resin was not observed to be in a well dispersed state. 39 322827 201139486 Example 6 (Aqueous polyurethane resin dispersion-4) Equipped with a stirrer, a nitrogen introduction tube 4,4'-methylene bis(cyclohexyl isocyanate) (trade name "Desmodur W", manufactured by Bayer) of polyisocyanate in a 4-neck separable flask with a heater. 111. gg a polyether diol having a number average molecular weight of 2000 (a product name "Terathane 2000", manufactured by Dupont Co., Ltd.) 250. 5 g, and 120. 7 g of the polyoxyalkylene alcohol A1 obtained in Example 1, A small amount of dibutyltin laurate (manufactured by Wako Pure Chemical Industries, Ltd.) as a reaction catalyst was added under a nitrogen atmosphere, and the reaction rate was 99% or more for 4 hours to obtain a polyurethane prepolymer. 440. 0g of the polymer was gradually added to 704 g of distilled water maintained under a strong stirring state to disperse it, and a chain extension reaction was carried out by adding 35.8 g of a 3 wt% aqueous solution of 2-indolyl-1'5-pentanediamine. The resulting dispersion is filtered through a 120 mesh stainless steel mesh. Polyuric Acid Brewing Resin Dispersion-4. The obtained aqueous polyurethane resin dispersion-4 has a solid content concentration of 38 4% and a viscosity at 20 ° C of 137 mPa · s. Stored in a sealed state at 40 ° C 2 During the month, no separation of the resin component was observed to maintain a good dispersion state. Example 7 (Aqueous Polyurethane Resin Dispersion-5) 4-neck detachable type equipped with a stirrer, a nitrogen gas introduction tube and a heater 4, 4,-methylene bis(cyclohexyl isocyanate) (trade name "Desmodur W", manufactured by Bayer Co., Ltd.) 47. 5 g, polyether 2 having a number average molecular weight of 2000 as a polyhydric alcohol The alcohol (trade name "Terathane 2000", manufactured by Dupont Co., Ltd.) l〇l. 5g ' and 90. Og of the polyoxyalkylene alcohol A2 obtained in Example 40 322827 201139486 2, added as a reaction catalyst under a nitrogen atmosphere A trace amount of dibutyltin laurate (Wako Pure Chemicals Co., Ltd.), the reaction rate of 99% or more after 4 hours of reaction to obtain a polyamine ester compound. The polyamic acid vinegar prepolymer 110·0g was slowly added to Keep it in 194g of distilled water in a strong state and disperse it. 3 wt% of an aqueous solution of 2-mercapto-1,5-pentamethylenediamine 8. 8 g was subjected to a bond extension reaction, and the resulting dispersion was filtered through a 120 mesh stainless steel mesh to obtain an aqueous polyurethane resin dispersion-5. The solid content concentration of the obtained aqueous polyurethane resin dispersion-5 was 36.2%, and the viscosity at 20 ° C was 161 mPa · s. During storage in the sealed state at 40 ° C for 2 months, no resin was observed. The separation of the fractions 'maintains a good dispersion state. Example 8 (Aqueous Polyurethane Resin Dispersion_6) In a 4-neck separable flask equipped with a stirrer, a nitrogen gas introduction tube and a heater, 4, 4'-arylene-based bis(cyclo) was added to the polyisocyanate. Hexyl isocyanate (trade name "Desmodur W", manufactured by Bayer Co., Ltd.) 61.6 g, polycarbonate diol having a number average molecular weight of 2000 as a polyol (trade name "ETERNACOLLUH-200", manufactured by Ube Industries, Ltd.) 133. 8 g, dihydromercaptopropionic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 3. 〇3 g, and 35.Og of N-mercaptopyrrolone (manufactured by Mitsubishi Chemical Corporation) of the polyoxyalkylene alcohol A1 obtained in Example 1. 25. Og 'The reaction temperature was adjusted to 92 to 90 ° C under a nitrogen atmosphere, and a small amount of dibutyltin laurate (manufactured by Wako Pure Chemical Industries, Ltd.) as a reaction catalyst was added to react for 4 hours, and the reaction rate was 99% or more. A polyamine prepolymer was obtained by adding 2.28 g of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) in a state of 75 ° C. 200 g of the polyurethane prepolymer of 41 322827 201139486 was slowly added to 397 g of distilled water maintained in a strong mixing state to be dispersed, and 35 wt% of ruthenium was added. 5, 戍 二 二 diamine aqueous solution 22. lg and carry out the bond extension reaction 'The resulting dispersion was passed through a 120 mesh stainless steel mesh to obtain an aqueous polyurethane resin dispersion -6. The solid content concentration of the obtained aqueous polyurethane resin dispersion-6 was 32. 9 〇 / 〇, and the viscosity at 20 ° C was 46 mPa · s » during storage for 4 months in a sealed state at 40 ° C, no seeing The separation of the resin fraction 'maintains a good dispersion state. Example 9 (Aqueous Polyurethane Resin Dispersion-7) 4,4,-indenylene double charged with polyisocyanate in a 4-neck separable flask equipped with a mixer, a nitrogen inlet tube and a heater (cyclohexyl isocyanate) (trade name "Desmodur W", manufactured by Bayer Co., Ltd.) 35. 2g, polycarbonate ester diol having a number average molecular weight of 2000 as a polyol (trade name "ETERNACOLLUHC50-200", manufactured by Ube Industries, Ltd. 76.4 g, 2.73 g of dimethylpropionic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 20.0 g of polyoxyalkylene alcohol A1 obtained in Example 1, N-methylpyrrolidone (manufactured by Mitsubishi Chemical Corporation) 14. 0g, the reaction temperature was adjusted to 92 to 90 Torr in a nitrogen atmosphere, and a small amount of dibutyltin laurate (manufactured by Wako Pure Chemical Industries, Ltd.) as a reaction catalyst was added, and after reacting for 4 hours, the reaction rate was 99% or more. A polyamine prepolymer was obtained by adding 1.31 g of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) in a state of 75 Å. The polyurethane prepolymer 120·〇g was slowly added to 203 g of distilled water maintained in a strong disturbing state to be dispersed. 'Addition of 35 wt% of 2-methyl-1,5-decane A chain extension reaction was carried out by using a diamine aqueous solution of 11.6 g, and the resulting aqueous polyurethane was found to have a resin dispersion of less than 205. The solid concentration of ~ is 33.2%, and the obtained aqueous polyurethane resin dispersion 7 has a viscosity at 20 ° C of 54 mPa · s. The separation in the sealed state at 40 ° C for 2 months was kept in a dispersed state of Liangzhu. Example 10 (Aqueous Polyurethane Resin Dispersion No. 8) Packed in a 4-neck separable flask equipped with a stirrer, an atmosphere introduction tube and a heater, 'Isophor, polyisocyanate, diisocyanate (trade name) "1", 8 ah, the company's café. 2g 'As the average number of the polyols 罝 1 just the poly diol (trade name "Caf, URETHME company" 78 | dimethyl (4) (Tokyo Chemical 2 g, and the methyl __ (Mitsubishi Chemical Co., Ltd.) 14. Gg, the reaction temperature is 8 in a nitrogen atmosphere. 〇至耽, “A small amount of butyltin yam salt (made by New Drugs Co., Ltd.) as an anti-living medium, when the reaction rate reaches 99 反应 after reacting 4*, then adding triethylamine in the state of 75 c (Wako Pure Chemical Co., Ltd.) l) 〇 9g to obtain a polyamine acid prepolymer. 100.0g of a prepolymer of polyuric acid preliminarily added to the water in the state of strong agitation to disperse, add people 35重量% of the hydrazine-based + pentane-sodium diamine aqueous solution 9. 5g and the chain extension reaction, the resulting dispersion through the 1 mesh sieve does not record steel mesh: Wei, Aqueous polyamine _ Resin dispersion -8. The total solidity of the poly-alkaline-polylipid _ fat dispersion is 31. The viscosity of 31 birds at 20 C is 47 mPa · s. 322827 43 201139486 40° in the closed state During the storage for 2 months, the separation of the resin was not observed, and the dispersion state was maintained. Example 11 (Aqueous polyurethane resin dispersion-9) 4 necks equipped with a stirrer, a nitrogen gas introduction tube, and a heater In the detachable flask, the 4, 4,--fluorenylene bis(cyclohexyl isocyanate) (trade name "Desmodur W", manufactured by Bayer Co., Ltd.) was added as a polyisocyanate. a polyether diol having a molecular weight of 2,000 (trade name "Terathane 2000", manufactured by Dupont Co., Ltd.), 20.5 g of dimercaptopropionic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.38 g of the polyoxyalkylene extended base obtained in Example 1. 120. 7g of alcohol A1 was adjusted to a temperature of 92 to 90 ° C under a nitrogen atmosphere. A small amount of dibutyl tin laurate (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a reaction catalyst, and the reaction rate reached 99 in 4 hours. More than 100% of the polyacetate prepolymer. The resulting is at 75. The urethane prepolymer 440·0g was slowly added to 7〇4g of distilled water maintained under strong stirring to disperse it, and 35% by weight of 2-methyl-1,5-pentanediamine was added. Aqueous solution 39. The chain extension reaction was carried out, and the obtained dispersion was filtered through a 12-inch sieve without a steel mesh to obtain an aqueous polyurethane resin dispersion -9. The obtained aqueous polyurethane resin was dispersed in a solid concentration of -9. It is 38. 2%, and the viscosity at 20 C is 163 mPa · s. During the storage for 40 months in the sealed state 40t, no separation of the resin component was observed, and the dispersion state was maintained. Example 12 (Aqueous Polyurethane Resin Dispersion - ίο) A 4-neck separable flask equipped with a stirrer, a nitrogen gas introduction tube and a heater, and a 4,4'-fluorenylene double (cyclic ring) filled with a polyisocyanate Hexyl isocyanate 322827 201139486 ester) (trade name "Desmodur W", manufactured by Bayer Co., Ltd.) 26 lg , polycarbonate ester diol having a number average molecular weight of 2000 as a polyol (trade name "ETERNACOLL UHC50-200", Ube 〇 2 \ 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 L L L L L L L 52 52 52 52 52 52 52 52 52 52 52 52 52 52 52 52 52 52 52 52 52 52 52 52 The temperature was adjusted to 92 to 90 ° C, and a small amount of dibutyltin laurate (manufactured by Wako Pure Chemical Industries, Ltd.) as a reaction catalyst was added, and the reaction rate was 99% or more after 4 hours, and then the polyamine prepolymer was transferred. The resulting will be at 75. Polyurethane prepolymer 100 in a bismuth state. 〇g is slowly added to 220 g of distilled water maintained under a strong stirring state to disperse it, and 35 wt% of 2-methyl-hydrazine, 5-pentane-one is added. A chain extension reaction was carried out with a fine aqueous solution of 8. 3 g, and the resulting dispersion was filtered through a 12-inch mesh stainless steel mesh to obtain an aqueous polyurethane resin dispersion. The obtained aqueous polyurethane resin dispersion-10 had a solid concentration of 31.0% at 20 ° C and a viscosity of 81 mPa · s. During storage in a sealed state at 40 ° C for 2 months, no separation of the resin was observed, and a good dispersion state was maintained. The aqueous polyurethane resin dispersions obtained in Examples 3 to 11 were coated on a resin substrate (trade name, "jUpil〇n", manufactured by Mitsubishi Engineering Plastics Co., Ltd.) and wood (birch). It was coated with a 50-gauge coating bar. The polycarbonic acid coated film sample was placed at 8 一 after one night. (: After drying for 20 minutes, the wood coating sample was dried in an environment of 25 ° C and a relative humidity of 50% for one week. The obtained coating film sample was subjected to a checkerboard tape peeling test in accordance with JIS D 0202-1988. The product name, "CT24", manufactured by Nichiban Co., Ltd., was peeled off on the film with the finger pad and peeled off. The judgment is based on the number of squares in which 1 square (1 45 322827 201139486 square is 2 mm square) The water-based polyurethane resin coating film was 100/100 when it was not peeled off, and was shown as OMOO when it was completely peeled off. The results are shown in Table 1. [Table 1] Example 3 Example 4 Example 5 Example 6 Implementation Example 7 Polycarbonate 100/100 100/100 100/100 52/100 26/100 Birch 100/100 100/100 100/100 100/100 100/100 Example 8 Example 9 Example 10 Example 11 Implementation Example 12 Polycarboester 100/100 100/100 100/100 97/100 26/100 Birch 100/100 100/100 100/100 100/100 100/100 Example 13 (Waterborne Polyurethane Resin Dispersion) -11) In a 4-neck separable flask equipped with a scrambler, a nitrogen inlet tube and a heater, 4, 4, - fluorene-based double polyisocyanate (cyclohexyl isocyanate) (trade name "Desmodur W", manufactured by Bayer Co., Ltd.) 61 · 6g, polycarbonate diol having a number average molecular weight of 2000 as a polyol (trade name "ETERNACOLL UH-200", manufactured by Ube Industries, Ltd. 1 。 。 。 。 。 115 115 115 115 115 115 115 115 115 115 63 63 63 63 63 63 63 63 63 63 63 63 63 63 63 63 63 63 63 63 63 63 63 63 63 63 63 63 63 63 63 63 63 63 63 63 Company system) 6()· 'In the nitrogen atmosphere, the reaction temperature was adjusted to 92 to 90 ° C, and a small amount of dibutyl tin laurate as a reaction catalyst was added (the reaction rate of the reaction with Wako Pure Chemical Co., Ltd. for 4 hours reached 99%). The viscosity of the polyurethane prepolymer obtained above is 2300 mPa · s at 70 t, and the viscosity is sufficiently low to be dispersed in water. The resulting polyurethane prepolymer of 7 5 ΐ state 46 322827 201139486 261. 6g was slowly added to 415g of distilled water maintained in a strong stirring state to disperse it, and a chain extension reaction was carried out by adding 25% by weight of a 25% by weight aqueous solution of 2-mercapto-1,5-pentanediamine. The resulting dispersion is filtered through a 120 mesh stainless steel mesh to obtain water. Polyamine acid ester resin dispersion -11. The resulting aqueous dispersion of a polyamine ester resin solid concentration was 31.3% -11, 20 ° C and the viscosity is 21 mPa · s. During storage in a sealed state at 40 ° C for 2 months, no separation of the resin was observed, and a good dispersion state was maintained. Further, since the solvent used in the production of the polyurethane prepolymer is a non-VOC carbonate, the VOC content is hardly detected in the obtained aqueous polyurethane resin dispersion. Example 14 (Aqueous Polyurethane Resin Dispersion-12) Water-based polymerization was carried out in the same manner as in Example 13 except that diethyl carbonate was replaced by diethyl carbonate (manufactured by Ube Industries, Ltd.) to prepare a prepolymer. Amine resin dispersion -12. The resulting prepolymer solution had a viscosity at 70 ° C of 2740 mPa · s and was sufficiently low in viscosity to be dispersed in water. The obtained aqueous polyurethane resin dispersion-12 had a solid content concentration of 31.3% and a viscosity at 20 ° C of 23 mPa · s. In the sealed state 4 (the period in which the TC was stored for 2 months, the separation of the resin was not observed, and the dispersion state was maintained. Further, the solvent used in the production of the polyurethane prepolymer was carbonic acid using a non-VOC substance. Since diethyl ester was absent, almost no VOC substance was detected in the obtained aqueous polyurethane resin dispersion. Comparative Example 1 47 322827 201139486 Prepolymerization was carried out in the same manner as in Example 13 except that dinonyl carbonate was used as a solvent. Solution: The viscosity of the prepolymer solution at 70 ° C is 38,300 mPa · s, lacking fluidity, and it is difficult to disperse in water. Comparative Example 2 4,4'-fluorenylene bis(cyclohexyl isocyanate) using polyisocyanate (product name "Desmodur W", manufactured by Bayer Co., Ltd.) 61.6 g, a polycarbonate diol having a number average molecular weight of 2,000 (a product name "ETERNACOLLUH-200", manufactured by Ube Industries, Ltd.), 233.8 g, Hydroxymercaptopropionic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 4. 00 g, dinonyl carbonate (manufactured by Ube Industries, Ltd.) 100. 0 g, a polyamine prepolymer was synthesized in the same manner as in Example 13. Prepolymer solution At 70° The viscosity of C is 47,200 mPa · s, and it lacks fluidity, and it is difficult to disperse in water. In Example 13 and Example 14, in a mixed solvent of carbonate and water which are not VOC materials, it is also stable and maintains dispersion state. Waterborne polyurethane resin dispersion. [Simple description of the diagram] No [Main component symbol description] No 48 322827

Claims (1)

(1) 201139486 VII. Patent application scope: 1. A polyoxyalkylene alcohol represented by the general formula (1) :[(R1〇)xi/<R2〇)nB-H [(r3o) ώ/ (R4〇) y2B~H [<R50)X3/(ReC〇Y3}>~ R7 where R is R6 each independently represents a linear branched-chain alkanediyl group having 2 to 10 carbon atoms, which may have an alicyclic structure or/and an aromatic ring structure, and R7 represents a linear or branched carbon number of 1 to 20. Alkyl, here 'R〗 #R2 ' R3: ^r4, r5 Off R6, X1, X2, Y1, Y2 means that X1+X2+Y1+Y2 is a number above 1 and not up to 10, Χ3, Υ3 Each of which represents a number from 0 to 135, XI and Yl 'Χ2 and γ2, and χ3 and γ3 may be the same or different numbers, and both XI and Υ1 may be 〇(zero), and both are not both 〇(zero), Χ3 and Υ3 are not all 〇(zero), [] is a block copolymer chain, or a random copolymer bond, or a homopolymer chain. The polyoxygen scales described in the above paragraph (4) are obtained by reacting an amine-based polyalkylene oxide having one NH2 group in the molecule with one or 1 322827 201139486 plural kinds of alkylene oxides. A polyoxyalkylene alcohol as described in the scope of the patent application, The alkylene oxide unit of the amine-based polyalkylene oxide comprises a pendant ethylenoxide unit. 4. The polyoxyalkylene alcohol according to any one of claims 3 to 3. Wherein the repeating unit of the polyoxyalkylene alcohol has a pendant ethylenoxide unit and/or a propylated oxide unit. 5. The poly-polymer according to any one of claims 4 to 4 The polyoxyalkylene alcohol of the present invention is an alkylene oxide or a propylated oxide, as described in claim 5, Wherein, at least one of R2〇, R30, r4〇, r5〇, (8) is an ethylidene oxide. 7. The polyoxygen extension according to any one of the above claims The alkyl alcohol, wherein the number average molecular weight is from 250 to 6,000. The polyoxyalkylene alcohol according to any one of the preceding claims, wherein 1 of the molecules is 1 Alkoxy end, and 2 hydroxyl ends. 9 · A polyurethane resin, at least the polyisocyanate and the scope of claim 1 to 8 The polyoxoalkyl alcohol described in the above item is obtained by the reaction of the polyoxoester resin according to claim 9 which is further reacted with a polyol having an acidic group. The polyurethane resin according to the first aspect of the invention, wherein the acidic group of the acid group-containing polyol is neutralized by an inert compound. The polyurethane resin according to any one of claims 9 to 11, which is obtained by reacting a polyoxyalkylene alcohol with a polyol other than an acid group-containing polyol. The polyurethane resin according to any one of claims 9 to 12, which is obtained by reacting with a chain extender. An aqueous polyurethane resin dispersion obtained by dispersing the polyurethane resin according to any one of claims 9 to 13 in an aqueous medium. The aqueous polyurethane resin dispersion according to claim 14, wherein the aqueous medium contains carbonate and water. 16. The aqueous polyurethane resin dispersion according to claim 14 or 15, wherein the carbonate is a group of dinonyl carbonate, diethyl carbonate and ethyl phthalate. One or more types of carbonated carbonates selected in the group. A coating agent comprising the aqueous polyurethane resin dispersion according to any one of claims 14 to 16. 18. A method for producing an aqueous polyurethane resin dispersion, which comprises, in an organic solvent containing carbonic acid vinegar, at least polyisocyanate, and any one of claims 1 to 8 The step of reacting the polyoxyalkylene alcohol, optionally containing an acidic group polyol, a polyoxyalkylene alcohol, and a polyol other than the acid group-containing polyol to obtain a polyurethane prepolymer , a step of dispersing a polyurethane prepolymer in an aqueous medium, 3 322827 201139486 and a step of reacting a polyurethane prepolymer with a chain length extender. 19. The method for producing an aqueous polyurethane resin dispersion according to claim 18, which has an organic compound containing a carbonate after the step of reacting the polyurethane prepolymer with the chain length extender Step 4 of the solvent distillation. 322827 201139486 ' IV. Designated representative figure: There is no drawing in this case (1) The representative representative figure of this case is: (). ' (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: :[(R1〇)xi/ (RzO)yiB—Η N f[(R3 〇)x2/(R4〇)Y2H-H (1) ;[(R5〇)x3/(R6〇)y3H~R7 322827