CN102858847A

CN102858847A - Polyoxyalkylene alcohol, polyurethane resin, and coating agent including same

Info

Publication number: CN102858847A
Application number: CN2011800098432A
Authority: CN
Inventors: 平川贵文
Original assignee: Ube Industries Ltd
Current assignee: Ube Corp
Priority date: 2010-02-19
Filing date: 2011-02-18
Publication date: 2013-01-02
Anticipated expiration: 2031-02-18
Also published as: JPWO2011102442A1; KR20130028069A; TW201139486A; JP5849945B2; CN102858847B; WO2011102442A1

Abstract

Disclosed is a novel polyoxyalkylene alcohol that is represented by general formula (1) and forms an isocyanate compound and a urethane bond. Also disclosed are a novel polyurethane resin that uses said polyoxyalkylene alcohol as a starting material, an aqueous polyurethane resin dispersion in which said polyurethane resin is dispersed within an aqueous medium, and a coating agent that includes said aqueous polyurethane resin dispersion. Additionally disclosed are an aqueous polyurethane resin dispersion in which the content of a volatile organic compound (a VOC material) has been reduced, and an aqueous polyurethane resin dispersion that is also dispersible in a mixed solvent comprising water and a carbonate that is not a VOC material.

Description

Polyether polyols and urethane resin and contain these coating agent

Technical field

The present invention relates to form the novel polyether polyols of urethane bond with isocyanate compound, this polyether polyols is dispersed in the water-medium as the new polyurethane resin of raw material, with this urethane resin and aqueous polyurethane resin dispersion and the coating agent that contains this aqueous polyurethane resin dispersion.And, the present invention relates to make aqueous polyurethane resin dispersion that the content of volatile organic compounds (VOC material) reduces, also dispersible aqueous polyurethane resin dispersion in the mixed solvent of the carbonic ether that contains non-VOC material and water.

Background technology

The urethane resin that reaction by polyvalent alcohol and isocyanate compound gets is the useful compound for injection molding, foam, coating, binding agent, synthetic leather, pigment tackiness agent etc.Except the urethane resin that is used for injection molding, foam applications etc., the situation that is typically used as with an organic solvent organic solvent as solvent and is urethane resin is more.

In recent years, from the viewpoint of carrying capacity of environment, wish to make the usage quantity of organic solvent to reduce, thereby carried out from being urethane resin to the transition of water as the waterborne polyurethane resin of dispersion medium with organic solvent as the organic solvent of solvent.Such waterborne polyurethane resin is generally speaking by using the external emulsification agent with urethane resin method of emulsification or import hydrophilic radical and the method for mechanically disperseing makes in polymer backbone in water mechanically in water.

For for the waterborne polyurethane resin that has imported hydrophilic radical in the polymer backbone, aspect hydrophilic radical, known (1) is by importing carboxyl on the carbamate skeleton, form ion pair with tertiary amine etc., thus the anionic property waterborne polyurethane resin that can be dispersed in water; (2) by tertiary amine being imported the carbamate skeleton, form ion pair with sour composition, thereby the cationic urethane resin that can disperse in water, (3) are passed through the Hydrophilicrto polyether fragments such as polyoxyethylene glycol are imported the carbamate main chain with catenary, thereby the nonionic urethane resin that can be dispersed in water (with reference to non-patent literature 1).

Wherein, as the nonionic urethane resin, proposed to import the material (with reference to patent documentation 1～3) of wetting ability polyalkylene oxide.In addition, about the polyoxy oxirane, proposed to make ammonia to be provided with amino (NH with the polyalkylene oxide reaction that comprises oxyethane, propylene oxide ₂Base) polyether polyols (with reference to patent documentation 4).

Need to prove, the situation that organic solvent uses in the manufacturing process of aqueous polyurethane resin dispersion is also more.Particularly, polyurethane prepolymer to synthesize the situation of carrying out in organic solvent more.Its objective is: reduce the viscosity of polyurethane prepolymer by adding organic solvent, thereby be easy to stir and react, perhaps improve the dispersiveness in water-medium.In the past, can be used as the organic solvent that such organic solvent uses and in fact only be the volatile organic compoundss (VOC material) such as acetone, vinyl acetic monomer, N-Methyl pyrrolidone (NMP).After also having proposed to make polyurethane prepolymer to be dispersed in the water-medium, above-mentioned organic solvent is heated up in a steamer etc., thereby make the VOC amount of substance in the end article aqueous polyurethane resin dispersion reduce (with reference to patent documentation 5).

Patent documentation

Patent documentation 1: the Deutsches Reichs-Patent application discloses communique No. 2141805

Patent documentation 2: Japanese kokai publication sho 50-2794 communique

Patent documentation 3: Japanese kokai publication hei 1-104612 communique

Patent documentation 4: Japanese kokai publication hei 3-181448 communique

Patent documentation 5: Japanese kokai publication hei 10-183060 communique

Non-patent literature

Non-patent literature 1: the exploitation of water-based coating material and application (CMC publish, 58 pages)

Summary of the invention

Invent problem to be solved

As mentioned above, polyether polyols can be as the raw material of waterborne polyurethane resin, even but the polyether polyols of patent documentation 4 reacts with polyisocyanate compound, also can react intensely with isocyanate group owing to amino, react and in obtaining the process of urethane resin, be difficult to control, only obtain hard carbamide resin, therefore, in the urgent need to forming with isocyanate compound the novel polyether polyols of urethane bond.In addition, the VOC amount of substance in the goods is reduced.

Problem of the present invention is, provide a kind of and can form the novel polyether polyols of urethane bond with isocyanate compound, this polyether polyols is dispersed in the water-medium as new polyurethane resin, this urethane resin of raw material and aqueous polyurethane resin dispersion and the coating agent that contains this aqueous polyurethane resin dispersion.And, the aqueous polyurethane resin dispersion that problem of the present invention is to provide the content that makes volatile organic compounds (VOC material) to reduce, its problem also is, is provided at the aqueous polyurethane resin dispersion that the mixed solvent of the carbonic ether that contains non-VOC material and water also can disperse.

Solve the required means of problem

The present invention finishes in order to solve above-mentioned problem, particularly, has following such formation.

(1) polyether polyols of a kind of general formula (1) expression.

In the formula,

R ¹～R ⁶Independently represent respectively the straight chain shape of carbon number 2～10 or alkane two bases of a chain, they can contain alicyclic structure and/or aromatic ring structure,

R ⁷The straight chain shape of expression carbon number 1～20 or the alkyl of a chain,

At this, R ¹≠ R ², R ³≠ R ⁴, R ⁵≠ R ⁶,

It is more than 1 and the number of less than 10 that X1, X2, Y1, Y2 represent to satisfy X1+X2+Y1+Y2,

X3, Y3 represent respectively 0～135 number,

X1 and Y1, X2 and Y2 and X3 and Y3 can be identical number, also can be different numbers,

X1 and Y1 all can be 0 (zero),

X2 and Y2 are not 0 (zero) simultaneously,

X3 and Y3 are not 0 (zero) simultaneously,

Can be the block copolymerization polymer chain in [], also can be the random copolymerization polymer chain, also can be the homopolymer chain.

(2) according to (1) described polyether polyols, it is to make to have 1 NH in 1 molecule ₂The amino polyalkylene oxide of base and the reaction of one or more oxiranes obtain.

(3) according to (2) described polyether polyols oxirane, it contains oxyethane.

(4) according to each described polyether polyols polyether polyols in (1)～(3), it contains ethylene oxide unit and/or propylene oxide units as repeating unit.

(5) according to each described polyether polyols, wherein R in (1)～(4) ¹O, R ²O, R ³O, R ⁴O, R ⁵O, R ⁶Among the O at least one is oxyethane or propylene oxide.

(6) according to (5) described polyether polyols, wherein, R ¹O, R ²O, R ³O, R ⁴O, R ⁵O, R ⁶Among the O at least one is oxyethane.

(7) according to each described polyether polyols in (1)～(6), its number-average molecular weight is 250～6000.

(8) according to each described polyether polyols in (1)～(7), it has 1 alkoxyl group end and 2 C-terminals in 1 molecule.

(9) a kind of urethane resin, it makes at least in polyisocyanates and (1)～(8) each described polyether polyols reaction and obtains.

(10) according to (9) described urethane resin, it further makes the polyol reaction that contains acidic-group obtain.

(11) according to (10) described urethane resin, wherein, the acidic-group that contains the polyvalent alcohol of acidic-group is neutralized by basic cpd.

(12) according to each described urethane resin in (9)～(11), it further makes except polyether polyols and other polyol reactions of containing the polyvalent alcohol of acidic-group and obtains.

(13) according to each described urethane resin in (9)～(12), it makes the chain extension agent reaction and obtains.

(14) a kind of aqueous polyurethane resin dispersion, it is dispersed in each described urethane resin in (9)～(13) in the water-medium and gets.

(15) according to (14) described aqueous polyurethane resin dispersion, wherein, water-medium contains carbonic ether and water.

(16) according to (14) or (15) described aqueous polyurethane resin dispersion, wherein, carbonic ether be selected from methylcarbonate, diethyl carbonate and the Methyl ethyl carbonate more than a kind.

(17) a kind of coating agent, it contains each described aqueous polyurethane resin dispersion in (14)～(16).

(18) a kind of manufacture method of aqueous polyurethane resin dispersion, it has:

In containing the organic solvent of carbonic ether, at least make each described polyether polyols in polyisocyanates and (1)～(8), the polyvalent alcohol that contains acidic-group that adds as required and add as required except polyether polyols and contain other polyol reactions the polyvalent alcohol of acidic-group, thereby obtain the operation of polyurethane prepolymer

Make polyurethane prepolymer be dispersed in operation in the water-medium, and

Make the operation of polyurethane prepolymer and chain extension agent reaction.

(19) according to the manufacture method of (18) described aqueous polyurethane resin dispersion, wherein, after the operation that polyurethane prepolymer and chain extension agent are reacted, has the operation that the organic solvent that will contain carbonic ether heats up in a steamer.

The invention effect

According to the present invention, can provide and can form the novel polyether polyols of urethane bond with isocyanate compound, this polyether polyols is dispersed in the water-medium as new polyurethane resin, this urethane resin of raw material and aqueous polyurethane resin dispersion and the coating agent that contains this aqueous polyurethane resin dispersion.And, according to the present invention, the aqueous polyurethane resin dispersion that can provide the content that makes volatile organic compounds (VOC material) to reduce also can be provided at the aqueous polyurethane resin dispersion that also can disperse in the mixed solvent of the carbonic ether that contains non-VOC material and water.

Embodiment

(polyether polyols (A))

The present invention relates to the polyether polyols (A) of general formula (1) expression,

In the formula,

R ¹～R ⁶Represent independently respectively the straight chain shape of carbon number 2～10 or alkane two bases of a chain, they can contain alicyclic structure and/or aromatic ring structure,

At this, R ¹≠ R ², R ³≠ R ⁴, R ⁵≠ R ⁶,

X3, Y3 represent respectively 0～135 number,

X1 and Y1 can be 0 (zero),

X2 and Y2 are not 0 (zero) simultaneously,

X3 and Y3 are not 0 (zero) simultaneously,

Can be for the block copolymerization polymer chain in [], also can be the random copolymerization polymer chain, also can be the homopolymer chain.

Polyether polyols (A) has 1 alkoxyl group end and 1 or 2 C-terminal in 1 molecule.

In general formula (1), R ¹O, R ²O, R ³O, R ⁴O, R ⁵O, R ⁶O represents respectively epoxy alkane unit.

In addition, at (R ¹O) _X1, (R ²O) _Y1, (R ³O) _X2, (R ⁴O) _Y2, (R ⁵O) _X3, (R ⁶O) _Y3In, be in the situation of the numeral more than 2 at X1～X3, Y1～Y3, expression has formed polyalkylene oxide.

[(R ¹O) _X1/ (R ²O) _Y1] can be R ¹O and R ²The random copolymerization polymer chain of O also can be the block copolymerization polymer chain, still, in X1 or Y1 one is in the situation of 0 (zero), expression homopolymer chain, in the situation that X1 and Y1 are 0, expression hydrogen atom (H) key and in nitrogen-atoms (N).

[(R ³O) _X2/ (R ⁴O) _Y2] can be R ³O and R ⁴The random copolymerization polymer chain of O, also can be the block copolymerization polymer chain, still, in X2 or Y2 one is in the situation of 0 (zero), expression homopolymer chain.

[(R ⁵O) _X3/ (R ⁶O) _Y3] can be R ⁵O and R ⁶The random copolymerization polymer chain of O, also can be the block copolymerization polymer chain, still, in X3 or Y6 one is in the situation of 0 (zero), expression homopolymer chain.

In general formula (1), key and be not in the situation of 0 (zero) in X1 or Y1 one of part nitrogen-atoms (N), following general formula (2) expression, expression hydrogen atom (H) key and in the Sauerstoffatom (O) of the epoxy alkane unit of end, thus the situation of hydroxyl formed endways.In addition, in the situation that X1 and Y1 are 0 (zero), the part of following general formula (2) expression represents hydrogen atom.

In general formula (1), key and represent that in part nitrogen-atoms (N), following general formula (3) expression X2 or Y2 are not 0 (zero) simultaneously, hydrogen atom key and in the Sauerstoffatom (O) of epoxy alkane unit, thus the situation of hydroxyl formed endways.

In general formula (1), key and in the part of the following general formula (4) of nitrogen-atoms (N) expression, both are not 0 (zero) simultaneously for expression X3 or Y3, the alkyl of the straight chain shape of carbon number 1～20 or a chain is R ⁷Key and in the Sauerstoffatom (O) of epoxy alkane unit, thus the situation of alkoxyl group formed endways.

In general formula (1), it is more than 1 and the number of less than 10 that X1, X2, Y1, Y2 represent to satisfy X1+X2+Y1+Y2.If the summation of X1, X2, Y1, Y2 is excessive, then in polyurethane backbone polyether structure to contain quantitative change many, therefore, there is the trend of the purposes of restriction polyether polyols (A) in the situation that exists the weathering resistance of urethane resin to reduce.

In general formula (1), X3 and Y3 represent respectively 0～135 number, preferably are respectively 0～80 number.X3 and Y3 are not 0 (zero) simultaneously, and the total value of the value of X3 and the value of Y3 is preferably 8～160.If total value is excessive, then the molecular weight as the polyoxy alkylidene chain of nonionic composition becomes excessive, therefore in the situation of the raw material that polyether polyols of the present invention (A) is used as aqueous polyurethane resin dispersion, there is the trend of the poor water resistance of filming that is made by aqueous polyurethane resin dispersion.In addition, in order to make the nonionic component content constant, and in the situation that the addition that makes polyether polyols (A) tails off, the quantity of the polyoxy alkylidene that existence is stretched out with catenary from the carbamate main chain tails off, the situation of prepolymer, the urethane resin dispersion stabilization variation in water-medium.Total value is preferably 8～160, more preferably 10～120.

In general formula (1), R ¹～R ⁶Represent independently respectively the straight chain shape of carbon number 2～10 or alkane two bases of a chain, they can contain alicyclic structure and/or aromatic ring structure.

As the straight chain shape of carbon number 2～10 or alkane two bases of a chain, for example be ethylidene (CH ₂CH ₂-), propylidene (CH (CH ₃) CH ₂-).

Alkane two bases of the straight chain shape of carbon number 2～10 or a chain can contain alicyclic structure and/or aromatic ring structure.At this moment, alicyclic structure and/or aromatic ring structure may reside in side chain, can also exist in the mode that alkane two bases are interrupted.As alicyclic structure, can enumerate the naphthenic hydrocarbon residue of carbon number 3～10 etc., such as enumerating tetramethylene residue, pentamethylene residue, hexanaphthene residue, bicycloheptane residue, diamantane residue etc.As aromatic ring structure, can enumerate benzene ring structure, naphthalene ring etc.Above-mentioned ring can for non-substituted, also can be by the replacements such as alkyl of carbon number 1～4.

In general formula (1), from the aspect that the reactivity of the hydroxyl of polyether polyols (A) uprises, R ¹O and R ³O is preferably oxygen propylidene chain (CH (CH ₃) CH ₂O-), R ²O and R ⁴O is preferably oxygen ethylidene chain (CH ₂CH ₂O-).Particularly preferably be: X1 and X2 are that 0 (zero) and Y1 and Y2 are 1～3.Further preferably: X1 and X2 are that 0 (zero) and Y1 and Y2 are 1.

In general formula (1), R ⁷The straight chain shape of expression carbon number 1～20 or the alkyl of a chain.

Polyether polyols of the present invention (A) have at least 2 can with the active hydrogen of isocyanic ester radical reaction (hydrogen of hydroxyl and/or amino hydrogen), can form urethane bond with isocyanate compound.

The number-average molecular weight of the polyether polyols among the present invention (A) is preferably 250～6,000.If in this scope, the wetting ability of the polyether polyols that then obtains (A) is abundant, and can reach the viscosity that demonstrates good operability.Number-average molecular weight more preferably 400～4000, be particularly preferably 500～2500.In this manual, number-average molecular weight is the value of utilizing hydroxyl value and/or amine value to obtain.

Polyether polyols among the present invention (A) for example is one or more oxiranes (a2) to be added be formed in to have endways 1 amino and the amino polyalkylene oxide (a1) take polyalkylene oxide as principal constituent, reacts to obtain.

In the formula, R ⁵, R ⁶, R ⁷, X3 and Y3 and general formula (1) same meaning.

In the formula, R ⁸And R ⁹Independent respectively is the straight chain shape of hydrogen atom or carbon number 1～8 or aliphatic alkyl and/or the aryl of a chain, can be by R ⁸And R ⁹Form alicyclic structure.

As the epoxy alkane unit of the polyalkylene oxide chain that has formed amino polyalkylene oxide (a1), can enumerate ethylene oxide unit, propylene oxide units, epoxybutane unit etc.Wherein, be preferably ethylene oxide unit and/or the propylene oxide units that can form the high oxirane chain of wetting ability.Be particularly preferably the amino polyalkylene oxide (a1) that the polyalkylene oxide chain is made of random copolymerization or the block copolymerization of oxyethane and propylene oxide.And then, be preferably the amino polyalkylene oxide (a1) that the polyalkylene oxide chain is made of the block copolymerization of oxyethane and propylene oxide, also being preferably the polyalkylene oxide chain is the amino polyalkylene oxide (a1) of polyethylene oxide.

For amino polyalkylene oxide (a1), the epoxy alkane unit except ethylene oxide unit be preferably less than 83 % by mole in whole epoxy alkane units, more preferably less than 60 % by mole, be particularly preferably less than 25 % by mole.

For amino polyalkylene oxide (a1), if all the ratio of the epoxy alkane unit except ethylene oxide unit in the epoxy alkane unit is too much, the trend that then has the wetting ability step-down of the polyether polyols that obtains, be not suitable as the polyvalent alcohol of the hydrophilic polyurethane resin such as aqueous polyurethane resin dispersion, have the trend of restriction purposes.

In with the situation of polyether polyols of the present invention (A) as the raw material of aqueous polyurethane resin dispersion, for amino polyalkylene oxide (a1), the epoxy alkane unit except ethylene oxide unit be preferably less than 83 % by mole in whole epoxy alkane units, more preferably less than 60 % by mole, be particularly preferably less than 25 % by mole.

An end of amino polyalkylene oxide (a1) is amino.Another end is the straight chain shape of carbon number 1～20 or the alkyl of chain, reactive low with oxirane (a2).

As amino polyalkylene oxide (a1), can use the compound that utilizes following known method for making to make, described method for making is substituted by amino method for the hydroxyl that utilizes ammonia etc. will make oxyethane, propylene oxide and the trimethyl carbinol carry out the Aethoxy Sklerol that addition polymerization gets, utilize ammonia etc. will make oxyethane, propylene oxide and methyl alcohol carry out addition polymerization and the hydroxyl of Aethoxy Sklerol be substituted by (for example Japanese kokai publication hei 3-181448 communiques) such as methods of amino.

In addition, as amino polyalkylene oxide (a1), also can use commercially available product.The ratio that for example can enumerate by the propylene oxide units (PO) in the polyalkylene oxide chain of HUNTSMAN company sale and ethylene oxide unit (EO) is JEFFAMINE (registered trademark) M-600 (number-average molecular weight: 600) of PO/EO=9/1, JEFFAMINE (registered trademark) M-1000 (number-average molecular weight: 1000) for PO/EO=3/19, JEFFAMINE (registered trademark) M-2005 (number-average molecular weight: 2000) for PO/EO=29/6, JEFFAMINE (registered trademark) M-2070 (number-average molecular weight: 2000) for PO/EO=10/31, Surfonamine B-200 (number-average molecular weight: 2000) etc. for PO/EO=95/5.

In above-mentioned commercially available amino polyalkylene oxide (a1), from obtaining the higher polyether polyols of wetting ability, be preferably JEFFAMINE (registered trademark) M-1000 or JEFFAMINE (registered trademark) M-2070.

Amino polyalkylene oxide (a1) has 1 primary amine, and the number-average molecular weight of described amino polyalkylene oxide (a1) is preferably 250～6000, more preferably 400～4000, is particularly preferably 500～2500.If the number-average molecular weight of amino polyalkylene oxide (a1) is too small, the trend that then exists the wetting ability of the polyether polyols (A) obtain to tail off, if number-average molecular weight is excessive, then exist the viscosity of the polyether polyols (A) that obtains to become too high, the trend of operability variation.

For amino polyalkylene oxide (a1), the epoxy alkane unit as amino polyalkylene oxide (a1) has is preferably the compound with the ethylene oxide unit more than 4.

In addition, amino polyalkylene oxide (a1) preferably except the active hydrogen of amino, does not have with isocyanate group and has reactive active hydrogen.

(oxirane (a2))

In the oxirane (a2) that reacts with amino polyalkylene oxide (a1), R ⁸And R ⁹Independent respectively is the straight chain shape of hydrogen atom or expression carbon number 1～8 or aliphatic alkyl and/or the aryl of a chain, R ⁸And R ⁹Can form alicyclic structure.As the straight chain shape of carbon number 1～8 or the aliphatic alkyl of a chain, for example can enumerate the straight chain shape of carbon number 1～8 or the alkyl of a chain, can enumerate methyl, ethyl etc.As aryl, can enumerate phenyl, naphthyl etc.As by R ⁸And R ⁹The alicyclic structure that forms can be enumerated cyclohexane structure etc.

As oxirane (a2), the non-ester ring type mono-epoxy compounds of aliphatics such as preferred use oxyethane, propylene oxide, butylene oxide ring, the aliphatics ester ring type mono-epoxy compounds such as epoxy cyclohexane etc.

The reaction of amino polyalkylene oxide (a1) and oxirane (a2) is by adding for 1 mole of amino polyalkylene oxide (a1) when stirring, 1 mole～6 moles doubly oxirane (a2), be preferably 2 moles～4 moles doubly oxirane (a2) and carry out, thereby can access oxirane (a2) addition polymerization in amino polyalkylene oxide (a1) and polyether polyols.

Amino polyalkylene oxide (a1) is-30 ℃～400 ℃, is preferably 0 ℃～350 ℃, more preferably 25 ℃～300 ℃ with the temperature of reaction of oxirane (a2).

In the reaction of amino polyalkylene oxide (a1) and oxirane (a2), can use solvent, also can not use solvent.As solvent, can enumerate toluene, methylene dichloride etc.

The reaction of amino polyalkylene oxide (a1) and oxirane (a2) can be with catalyzer, also can carry out with catalyzer.In the situation that use catalyzer, as catalyzer, can enumerate the basic catalysts such as sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood.The addition of catalyzer is for the total amount of amino polyalkylene oxide (a1) and oxirane (a2), for 1ppm～5.0 % by weight, be preferably the scope of 5ppm～1.0 % by weight.But, in with the situation of polyether polyols of the present invention (A) as the raw material of aqueous polyurethane resin dispersion, never need the viewpoint of removing operation of catalyzer to set out, preferably do not use the mode of catalyzer to carry out the reaction of amino polyalkylene oxide (a1) and oxirane (a2).

Reaction pressure during the reaction of amino polyalkylene oxide (a1) and oxirane (a2) is not particularly limited, and for the oxirane (a2) that prevents from adding is spilled over to outside the reaction system with unreacted state, preferably implements reaction at pressurized conditions.

Oxirane (a2) can be put in the reaction vessel with amino polyalkylene oxide (a1), also can in advance amino polyalkylene oxide (a1) be put in the reaction vessel, again to wherein dripping or adding off and on oxirane (a2).

For the reaction of amino polyalkylene oxide (a1) with oxirane (a2), in the situation that use basic catalyst, after reaction finishes, preferably remaining basic catalyst is removed.As the method for removing of basic catalyst, can enumerate and add the method that neutralizes, the method for lentamente reaction solution being removed basic catalyst by the cationic exchange resin etc. with the acid such as the phosphoric acid of the alkali equivalent of adding.

And then, in order to remove remaining moisture and the unreacted oxirane (a2) in the reaction system, preferably under for example 130 ℃, the condition of 1.0KPa, dewatered 0.5～2 hour.

(urethane resin)

Urethane resin of the present invention obtains by polyisocyanates (D) and above-mentioned polyether polyols (A) are reacted.The manufacture method of urethane resin is not particularly limited, and can enumerate the single stage method that whole raw materials is reacted once, the prepolymer method that makes polyether polyols (A) behind the manufacturing prepolymer chain extension agent be reacted with polyisocyanates (D) reaction.Viewpoint from molecular weight of being easy to control urethane resin etc. is preferably prepolymer method.

Urethane resin can adopt the aqueous polyurethane resin dispersion, urethane foam, the thermoplastic polyurethane resin that are dispersed in the water-medium, be dispersed or dissolved in the various forms such as polyurethane resin solution in the organic solvent.

(polyisocyanates (D))

Polyisocyanates among the present invention (D) is not particularly limited so long as have the polyisocyanates of the isocyanate group more than 2 get final product in 1 molecule.

Particularly, can enumerate 1, the 3-phenylene vulcabond, 1, the 4-phenylene vulcabond, 2,4-toluylene group diisocyanate (TDI), 2,6-toluylene group diisocyanate, 4,4 '-diphenylene methane vulcabond (MDI), 2, the 4-diphenylmethanediisocyanate, 4,4 '-two isocyanato-biphenyl, 3,3 '-dimethyl-4,4 '-two isocyanato-biphenyl, 3,3 '-dimethyl-4,4 '-two isocyanato-ditans, 1, the 5-naphthalene diisocyanate, 4,4 ', 4 "-and triphenylmethane triisocyanate; an isocyanato-phenyl sulfonyl isocyanic ester; to isocyanato-phenyl sulfonyl isocyanic ester; phenylene two (isopropyl cyanic acid) the aromatic polyisocyanate compound such as (TMXDI); Ethylidene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), ten dimethylene diisocyanates, 1,6,11-undecane triisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, lysinediisocyanate, 2,6-two isocyanato-methylhexanoic acid esters, two (2-isocyanatoethyl) fumarate, two (2-isocyanatoethyl) carbonic ether, 2-isocyanatoethyl-2, the aliphatic polyisocyanate compounds such as 6-two isocyanato-capronates; Isophorone diisocyanate (IPDI), 4,4 '-dicyclohexyl methane diisocyanate (hydrogenation MDI), tetrahydrobenzene vulcabond, tetrahydrotoluene vulcabond (hydrogenation TDI), two (2-isocyanatoethyl)-4-tetrahydrobenzene-1,2-dicarboxylic ester, 2,5-norbornene alkyl diisocyanate, 2, the ester ring type polyisocyanate compounds such as 6-norbornene alkyl diisocyanate etc.Above-mentioned polyisocyanates can be used alone or two or more kinds may be used.

Isocyanate group in 1 molecule of polyisocyanates is generally 2, but in the scope of gelation does not occur urethane resin of the present invention, also can use the polyisocyanates with 3 above isocyanate group as triphenylmethane triisocyanate.

In polyisocyanates, from controlling reactive viewpoint, be preferably isophorone diisocyanate (IPDI), HMDI (hydrogenation MDI), phenylene two (isopropyl isocyanate) (TMXD).

In the manufacturing of urethane resin of the present invention, can and with the polyvalent alcohol (B) that contains acidic-group and and use except polyether polyols (A) and contain the polyvalent alcohol (B) of acidic-group other polyvalent alcohol (below be also referred to as " other polyvalent alcohol ") (C).

(polyvalent alcohol (B) that contains acidic-group)

As the polyvalent alcohol (B) that contains acidic-group of the present invention, as long as in 1 molecule, having hydroxyl more than 2 and the polyvalent alcohol that contains acidic-group of the acidic-group more than 1, be not particularly limited.As acidic-group, can enumerate carboxyl, alkylsulfonyl etc. as the functional group of Bronsted acid performance function.Acidic-group can be phosphate, phenol hydroxyl etc.

Particularly, can enumerate 2,2-dimethylol propionic acid, 2, the dimethylolalkanoic acids such as 2-dimethylolpropionic acid; N, N-bicine N-, N, N-dihydroxy ethyl L-Ala, 3,4-dihydroxyl butane sulfonic acid, 3,6-dihydroxyl-2-toluenesulphonic acids etc.The above-mentioned polyvalent alcohol that contains acidic-group can be used alone or two or more kinds may be used.

In containing the polyvalent alcohol of acidic-group, be easy to viewpoint from starting with, be preferably 2,2-dimethylol propionic acid, 2, the 2-dimethylolpropionic acid.

(other polyvalent alcohol (C))

As other the polyvalent alcohol (C) among the present invention, as long as be the polyol compound except polyether polyols (A) and the above-mentioned polyvalent alcohol (B) that contains acidic-group, be not particularly limited, such as low molecular polylol (C2) of the macromolecule polyol that can use number-average molecular weight 400～5000 (C1) and/or number-average molecular weight less than 400 etc.Particularly preferably also with above-mentioned high molecular weight polyols (C1) and low molecular weight polyols (C2).

In the situation that also with high molecular weight polyols (C1) and low molecular weight polyols (C2), ratio as the macromolecule polyol (C1) in other the total amount of polyvalent alcohol (C), be not particularly limited, preferred high molecular weight polyols (C1) is 80～99 % by weight, 90～98 % by weight more preferably.

As macromolecule polyol (C1), can enumerate polycarbonate diol, polycarbonate esterdiol, polycarbonate ether glycol, polyester glycol, polyester ether two pure and mild polyether glycols etc.Wherein, from the viewpoint good with the adaptation of polycarbonate resin base material, preferred use be selected from polycarbonate diol, polycarbonate esterdiol, the polyester glycol more than a kind.

Polycarbonate diol is not particularly limited, and can use the polycarbonate diol that makes by common manufacture method.Particularly, can enumerate by making diol compound (ethylene glycol, Isosorbide-5-Nitrae-butanediol, 1,5-pentane diol, neopentyl glycol, 1,6-hexane diol, 1,8-octane glycol, nonane glycol, 1,10-decane glycol, 1,12-dodecanediol, Isosorbide-5-Nitrae-cyclohexane diol etc.They can be used alone or two or more kinds may be used) with the carbonate products reactions such as methylcarbonate, diethyl carbonate, ethylene carbonate, carry out dealcoholation and the polycarbonate diol that makes; Polycarbonate diol that makes in order to the method with the transesterify of above-mentioned diol compound and diaryl carbonate (such as diphenyl carbonate etc.) etc.

The concrete example of polycarbonate diol can be enumerated the polycarbonate diol (such as the polycarbonate diol of polytetramethylene carbonic ether glycol, poly-5-methylene carbonate glycol, the own esterdiol of polymerized thylene carbonate, nonanediol, the carbonic ether of decanediol, the polycarbonate of dodecanediol etc.) of the straight chain shape alkylidene group with carbon number 4～12; Polycarbonate diol (such as the polycarbonate diol of 2-methylbutane glycol, the polycarbonate diol of 2-ethyl butanediol, the polycarbonate diol of neopentyl glycol, the polycarbonate diol of 2-methylpentane glycol, the polycarbonate diol of 3-methylpentane glycol etc.) with chain alkylidene group of carbon number 4～12; With their multipolymer.

Polyester glycol is not particularly limited, and can use the material that utilizes common manufacture method to make.Particularly, can enumerate by making diol compound (compound as hereinbefore) and dicarboxylic acid compound (aliphatic dicarboxylic acid (succsinic acid, hexanodioic acid, nonane diacid, sebacic acid, dodecanedioic acid, dimeracid etc.), aromatic dicarboxylic acid (terephthalic acid, m-phthalic acid, phthalic acid etc.) etc.They can be used alone or two or more kinds may be used) react (condensation) and compound; By making lactone (6-caprolactone, gamma-butyrolactone, γ-valerolactone etc.They can be used alone or two or more kinds may be used) carry out ring-opening polymerization and compound etc.

Polyether glycol is not particularly limited, and can use the compound that utilizes common manufacture method to make.Particularly, can enumerate by not using catalyzer or in the presence of catalyzer (basic catalyst, amine series catalysts, an acidic catalyst) rear half stage of oxirane addition (particularly), at normal pressure or add and depress, with 1 stage or a plurality of stage, carry out to addition oxirane (oxyethane, propylene oxide, 1 such as diol compounds (as hereinbefore), 2-, 2, the epoxy material of 3-or 1,3-butylene oxide ring, tetrahydrofuran (THF), Styryl oxide, alpha-olefin, epoxy chloropropane etc.They can be used alone or two or more kinds may be used), thus the compound that obtains etc.Need to prove, in the situation that use the addition mode of oxirane more than 2 kinds can be block-wise, also can be random shape.

As low molecular polylol (C2), can enumerate polyalcohols (2 yuan of alcohol (ethylene glycol, 1 for example of carbon number 2～15,3-propane diol, 2-methyl isophthalic acid, 3-propane diol, 2,2-dimethyl-1,3-propane diol, 2-butyl-2-ethyl-1,3-propane diol, Isosorbide-5-Nitrae-butanediol, 1,5-pentane diol, 3-methyl isophthalic acid, 5-pentane diol, 1, the aliphatic diols such as 6-hexane diol, alkane (carbon number 7～22) glycol, Diethylene Glycol, triethylene glycol, TEG; 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexane diol, 1, two (hydroxyethyl) hexanaphthenes, 2 of 4-, 7-norbornane glycol, tetrahydrofurandimethanol, 2, two (the methylol)-Isosorbide-5-Nitrae-Evil dioxanes of 5-etc. have the glycol etc. of the ester ring type structure of carbon number 6～12); Alcohol more than 3 yuan (such as glycerol, TriMethylolPropane(TMP), Sorbitol Powder etc.); The oxirane of above-mentioned polyvalent alcohol (EO and/or PO) low mole affixture (not enough Mn400) etc.).

(polyurethane prepolymer (E))

In the manufacture method of urethane resin of the present invention, in the situation that adopt prepolymer method, can be via making urethane resin as the polyurethane prepolymer (E) of intermediate.

The compound of polyurethane prepolymer (E) for polyether polyols (A), other polyvalent alcohol (C) and polyisocyanates (D) reaction are obtained, the polyvalent alcohol (B) that contains acidic-group is any composition.

The mole number of the isocyanate group of polyisocyanates (D) is preferably 1.01～2.5, more preferably 1.2～2.2, is particularly preferably 1.2～2.0 with respect to the ratio of the mole number of polyether polyols (A), the polyvalent alcohol that contains acidic-group (B) of any composition of conduct and the active hydrogen that other polyvalent alcohol (C) has.

With polyether polyols (A), be made as in the situation of 100 weight parts as any gross weight of the polyvalent alcohol that contains acidic-group (B), other polyvalent alcohol (C) and the polyisocyanates (D) of composition, the weight part that contains the polyvalent alcohol (B) of acidic-group be preferably 0.01～30 weight part, more preferably 0.05～25 weight part, be particularly preferably 0.1～15 weight part.If it is too much to contain the weight part of polyvalent alcohol (B) of acidic-group, then there is the trend of the patience variation of the urethane resin that obtains.

If the mole number of active hydrogen is too much with respect to the mole number of the isocyanate group of polyisocyanates (D), then exists the viscosity of the polyurethane prepolymer (E) that obtains to uprise, stirring or the difficult trend of dispersion change in water-medium.In addition, if the mole number of active hydrogen is very few with respect to the mole number of isocyanate group, then unreacted polyisocyanates (D) remains in the reaction system in large quantities, with the reaction of above-mentioned chain extension agent in the heating quantitative change many, therefore, be difficult to control temperature of reaction, have the trend that generates the gel urethane resin.

In the manufacturing of urethane resin, polyurethane prepolymer (E), contain in use in the situation of polyvalent alcohol (B) of acidic-group, in the few situation of the mole number of the above-mentioned polyether polyols of mole ratio (A) that contains the polyvalent alcohol of acidic-group (B), acidic-group in the polyvalent alcohol (B) that contains acidic-group even do not neutralize, also can be in water-medium disperse aqueous urethane resin dispersion stably.Namely, from omit and the aspect of operation, in the manufacturing of urethane resin, polyurethane prepolymer (E), preferably use the polyvalent alcohol (B) that contains acidic-group according to the few mode of mole number of the mole ratio polyether polyols (A) that makes the polyvalent alcohol (B) that contains acidic-group.

In the situation that obtain polyurethane prepolymer (E), polyether polyols (A), the conduct arbitrarily reaction of the polyvalent alcohol that contains acidic-group (B), other polyvalent alcohol (C) and the polyisocyanates (D) of composition can different order make (A), arbitrarily (B), (C) and (D) reaction of composition, also can with (A), as arbitrarily (B) and (C) mixing of composition, react with (D) again.

Containing of polyether polyols unit in the polyurethane prepolymer (E) is proportional in weight basis, is preferably 3～60%.If the polyether polyols unit in the polyurethane prepolymer (E) is very few, the wetting ability step-down that then has the urethane resin that obtains, or in the situation that utilize polyurethane prepolymer (E) to make the situation that the above-mentioned polyurethane prepolymer of aqueous polyurethane resin dispersion (E) is difficult to disperse in water-medium.On the other hand, if the above-mentioned polyether polyols unit in the polyurethane prepolymer (E) is too much, then there is the trend of the weather resistance step-down of urethane resin.The polyether polyols unit contain proportional more preferably 8～40%.Need to prove, in the present invention, so-called polyether polyols unit is the part after the hydrogen atom of the hydroxyl of polyether polyols is removed.

When polyether polyols (A), the polyvalent alcohol that contains acidic-group (B) as any composition, other polyvalent alcohol (C) and polyisocyanates (D) are reacted, also can use catalyzer.

Catalyzer is not particularly limited, such as the salt that can enumerate the metals such as tin series catalysts (tin trimethyl laurate, dibutyltin dilaurate etc.), plumbous series catalysts (lead octoate 36 etc.) and organic acid and mineral acid, Organometallic derivatives, amine series catalysts (triethylamine, N-ethylmorpholine, triethylenediamine etc.), diazabicyclo undecylene (diazabicycloundecene) series catalysts etc.Wherein, from reactive viewpoint, be preferably dibutyltin dilaurate.

As making polyether polyols (A), the conduct arbitrarily polyvalent alcohol that contains acidic-group (B), other polyvalent alcohol (C) and the temperature of reaction of polyisocyanates (D) when reacting of composition, be not particularly limited, be preferably 40～150 ℃.If reaction temperature is spent low, then raw material does not dissolve sometimes, or the viscosity of the polyurethane prepolymer that obtains (E) uprises and can't stir fully.In addition, if temperature of reaction is too high, then sometimes produce undesirable conditions such as causing side reaction.More preferably 60～120 ℃ of temperature of reaction.

Polyether polyols (A), as the reaction of the arbitrarily polyvalent alcohol that contains acidic-group (B), other polyvalent alcohol (C) and the polyisocyanates (D) of composition can be solvent-free or the adding organic solvent carry out.

As organic solvent, be preferably the organic solvent that contains carbonic ether.As carbonic ether, can use the dialkyl carbonates such as methylcarbonate, diethyl carbonate, Methyl ethyl carbonate, dipropyl carbonate, dibutyl carbonate, the alkylene carbonate diester such as ethylene carbonate, the alkyl aryl carbonate esters such as the diaryl carbonates such as diphenyl carbonate, carbonic acid methyl phenyl ester etc.In above-mentioned carbonic ether, be preferably dialkyl carbonate, further more preferably in low-boiling methylcarbonate, diethyl carbonate, the Methyl ethyl carbonate more than at least a kind.

As organic solvent, except carbonic ether, also can add acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), tetrahydrofuran (THF), diox, dimethyl formamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, N-ethyl pyrrolidone, vinyl acetic monomer etc.Wherein because acetone, methyl ethyl ketone, vinyl acetic monomer polyurethane prepolymer is dispersed in water and the chain lengthening reaction after can remove by the heating decompression, therefore than other organic solvent more preferably.In addition, N-Methyl pyrrolidone, N-ethyl pyrrolidone play a role as membrane producing promoter when making the filming of aqueous polyurethane resin dispersion, thereby preferred.

Be replaced into carbonic ether by the part with organic solvent, thereby can reduce the VOC amount of substance in the goods.In addition, because can eliminate VOC material in the goods, so preferably only use carbonic ether as organic solvent.

The addition of organic solvent is preferably 3～35 weight parts with polyether polyols (A), be made as in the situation of 100 weight parts as any gross weight of the polyvalent alcohol that contains acidic-group (B), other polyvalent alcohol (C) and the polyisocyanates (D) of composition.

As mentioned above, can when making prepolymer, in system, add organic solvent, add before also can and being dispersed in the water-medium after making prepolymer.

(basic cpd (F))

For urethane resin of the present invention, contain in use in the situation of polyvalent alcohol (B) of acidic-group, the acidic-group of the polyvalent alcohol (B) that contains acidic-group of can neutralizing can not neutralize.In order to improve the dispersiveness of urethane resin in water-medium, preferably utilize in the basic cpd (F) and acidic-group.

From the acidic-group of the polyvalent alcohol that contains acidic-group (B) in the urethane resin, be less than in the situation of mole of polyether polyols (A) with the mole number of the proton of alkali substance reaction, during the tertiary amine of polyether polyols has and the effect of acidic-group, therefore, can use basic cpd (F).

For the neutralization of the acidic-group that has used basic cpd (F), can the polyvalent alcohol (B) that contain acidic-group be carried out again after reacting with polyether polyols (A), other polyvalent alcohol (C), polyisocyanates (D).

Make aqueous polyurethane resin dispersion in the situation that utilize prepolymer method, can in advance basic cpd (F) be mixed with polyurethane prepolymer (E), it is dispersed in the water-medium, also can in advance basic cpd (F) be mixed with water-medium, polyurethane prepolymer (E) is dispersed in the water-medium, can also when making polyurethane prepolymer (E) be dispersed in the water-medium, basic cpd (F) be added in the water-medium.

As basic cpd (F), such as enumerating the organic amines such as Trimethylamine 99, triethylamine, tri-isopropyl amine, Tributylamine, trolamine, N methyldiethanol amine, N-phenyldiethanol-amine, dimethylethanolamine, diethylethanolamine, N-methylmorpholine, pyridine; The inorganic base such as sodium hydroxide, potassium hydroxide, ammonia etc.In above-claimed cpd, be preferably organic amine, more preferably the tertiary amine such as triethylamine.

The acidic-group of the polyvalent alcohol (B) that basic cpd (F) is that urethane resin is made with respect to being used for, come self-contained acidic-group, for the mole number of the proton of alkali substance reaction, preferably in the scope of 0～3.0 times of mole, use, more preferably the scope of 0～1.5 times of mole.

(chain extension agent (G))

Chain extension agent (G) just is not particularly limited so long as have the compound that has reactive functional group with the isocyanate group of polyurethane prepolymer (E).

As chain extension agent (G), for example can enumerate quadrol, 1,4-butanediamine, 2-methyl isophthalic acid, 5-pentamethylene diamine, 1,4-butanediamine, 1,6-hexanediamine, Isosorbide-5-Nitrae-hexanediamine, 3-amino methyl-3,5,5-trimethyl cyclohexylamine, 1, two (amino methyl) hexanaphthenes of 3-, benzene dimethylamine, piperazine, 2, the amine compound such as 5-lupetazin, diethylenetriamine, Triethylenetetramine (TETA), ethylene glycol, propylene glycol, 1,4-butyleneglycol, 1, the diol compounds such as 6-hexylene glycol, the polyalkylene glycols take polyoxyethylene glycol as representative, water etc.They can use separately, and also two or more kinds may be used.

The addition of chain extension agent (G) with respect in the polyurethane prepolymer of gained as for isocyanate group 1 equivalent of chain extension starting point, be preferably 1 equivalent following, more preferably for isocyanate group 1 equivalent, be 0.5～0.99 equivalent.Adding in the situation of chain extension agent (G) in the mode that for isocyanate group 1 equivalent, surpasses 1 equivalent, existence by chain extension the molecular weight of urethane resin reduce the urethane resin of coating gained or the aqueous polyurethane resin dispersion of gained and the trend of the strength decreased of filming that obtains.

In the situation that make aqueous polyurethane resin dispersion, the interpolation order of chain extension agent (G) can carry out polyurethane prepolymer after being dispersed in water, also can be for carrying out simultaneously with dispersion.Chain extension also can utilize water to carry out.In this case, have the effect of chain extension agent concurrently as the water of dispersion medium.

Temperature of reaction as making polyurethane prepolymer (E) with chain extension agent (G) reaction for example is preferably 0～80 ℃, more preferably 0～60 ℃.

Aqueous polyurethane resin dispersion among the present invention is the dispersion that urethane resin is dispersed in get in the water-medium.

As water-medium, can enumerate the blending agent of water, water and hydrophilic organic solvent etc.As water, such as enumerating tap water, ion-exchange, distilled water, ultrapure water etc.As hydrophilic organic solvent, except can adding the organic solvent in the polyurethane prepolymer to, can enumerate the low-grade monobasic alcohols such as methyl alcohol, ethanol, propyl alcohol; The polyvalent alcohol such as ethylene glycol, glycerol; The hydrophilic organic solvent of the non-proton property such as N-methylmorpholine, dimethyl sulfoxide (DMSO), dimethyl formamide, N-Methyl pyrrolidone, N-ethyl pyrrolidone etc.As the amount of the hydrophilic organic solvent in the water-medium, be preferably 0～20 % by weight.

In the present invention, can use contain carbonic ether and water blending agent as water-medium.As carbonic ether, can enumerate methylcarbonate, diethyl carbonate, Methyl ethyl carbonate etc.

Except carbonic ether and water, can also add above-mentioned hydrophilic organic solvent, but from making VOC material such viewpoint that tails off, be preferably the blending agent that is consisted of by carbonic ether and water.As the ratio of the carbonic ether in the water-medium, when being made as 100 weight part, water-medium integral body is preferably 1～15 weight part.If the content of carbonic ether is too much, then carbonic ether separates from goods sometimes.

(aqueous polyurethane resin dispersion)

In the situation that make aqueous polyurethane resin dispersion, make polyether polyols (A), react and the operation that obtains polyurethane prepolymer (E) can be carried out under inert gas atmosphere as the arbitrarily polyvalent alcohol that contains acidic-group (B), other polyvalent alcohol (C) and the above-mentioned polyisocyanates (D) of composition, also can under air atmosphere, carry out.

With in the basic cpd (F) and the operation of polyurethane prepolymer (E) can under inert gas atmosphere, carry out, also can under air atmosphere, carry out.

The operation that makes polyurethane prepolymer (E) obtain waterborne polyurethane resin with chain extension agent (G) reaction can be carried out under inert gas atmosphere, also can carry out under air atmosphere.

The method that waterborne polyurethane resin is disperseed is not particularly limited, such as enumerating following method: in the water-medium that utilizes homomixer or clarifixator etc. to carry out stirring, add the method for polyurethane prepolymer or polyurethane prepolymer solution, in the polyurethane prepolymer that utilizes homomixer or clarifixator etc. to carry out stirring, add the method for water-medium etc.

For the reaction of polyurethane prepolymer (E) and chain extension agent (G) is obtained for the waterborne polyurethane resin, can under cooling, add chain extension agent (G) and react, also can under the condition of heating of 60 ℃ of following degree, promote to react and carry out

The ratio of the urethane resin in the aqueous polyurethane resin dispersion of the present invention (ratio of solids component) is preferably 5～60 % by weight, 20～50 % by weight more preferably.

By making aqueous polyurethane resin dispersion lower as for decompression, above-mentioned organic solvent can also be heated up in a steamer.Heating up in a steamer of organic solvent can be carried out in heating, stirring.

In addition, can be according to its purpose and purposes in waterborne polyurethane resin of the present invention, can suitably cooperate various additives, such as softening agent, whipping agent, defoamer, flow agent, mould inhibitor, rust-preventive agent, matting agent, fire retardant, thixotropic agent, tackifier, thickening material, lubricant, static inhibitor, tensio-active agent, response delay agent, antioxidant, UV light absorber, hydrolysis-resisting agent, weather-proof stablizer, dyestuff, mineral dye, pigment dyestuff, pigment extender, solidifying agent, anti-seam agent etc.The mixing ratio of above-mentioned various additives can suitably be selected according to its purpose and purposes.

Coating agent of the present invention contains aqueous polyurethane resin dispersion of the present invention, and can obtain by adding above-mentioned additive as required.

Coating agent of the present invention such as can utilize the known casting method such as laminating, directly the known coating method such as coating method is coated base material, coating process can suitably be selected according to its purpose and purposes.

Need to prove, aqueous polyurethane resin dispersion of the present invention is such as performing well in the various coating purposes such as automobile, e-machine, building materials, artificial leather.

In the situation that use carbonic ether as water-medium, the manufacture method of aqueous polyurethane resin dispersion of the present invention has following operation at least.Following operation (γ) can be carried out successively with operation (δ), also can carry out simultaneously.

In containing the organic solvent of carbonic ether, at least make polyisocyanates (D) and polyether polyols (A), the polyvalent alcohol that contains acidic-group (B) that according to circumstances adds, and other polyvalent alcohol (C) reaction, thereby obtain the operation (α) of polyurethane prepolymer (E);

Make polyurethane prepolymer (E) be dispersed in operation (γ) in the water-medium;

The operation (δ) that polyurethane prepolymer (E) and chain extension agent (G) are reacted.

As the raw material of waterborne polyurethane resin of the present invention, contain in use in the situation of polyvalent alcohol (B) of acidic-group, when its acidic-group of neutralization, have following operation.Following operation (γ) and operation (δ) can be carried out successively, also can carry out simultaneously.

In containing the organic solvent of carbonic ether, at least make polyisocyanates (D), polyether polyols (A), contain polyvalent alcohol (B) and other polyvalent alcohol (C) reaction of acidic-group, thereby obtain the operation (α) of polyurethane prepolymer (E).

Utilize in the basic cpd (F) and the operation (β) of the acidic-group of polyurethane prepolymer (E).

Make polyurethane prepolymer (E) be dispersed in operation (γ) in the water-medium.

Embodiment

Below, with reference to embodiment and comparative example, the present invention is further specifically described, but the present invention is not limited to this.Need to prove, " % " is weight basis just as long as no mentioning especially.

The mensuration of each amine value is carried out according to following method.

＜total amine value 〉

For total amine value, be to use perchloric acid-Glacial acetic acid titrating solution (0.1N), Viola crystallina indicator, Glacial acetic acid solvent, by the potential difference titration obtain with in and the mg number of the potassium hydroxide of the amount equivalent of the needed perchloric acid of 1g sample.

＜tertiary amine value 〉

For tertiary amine value, be use perchloric acid-Glacial acetic acid titrating solution (0.1N), Viola crystallina indicator, Glacial acetic acid and acetic anhydride are mixed with 1: 9 volume ratio and mixed solvent, by the potential difference titration obtain with in and the mg number of the potassium hydroxide of the needed perchloric acid equivalent of 1g sample.

The total amount of＜secondary amine value and tertiary amine value 〉

In sample, add salicylic aldehyde, make itself and primary amine reaction, utilize acidic alcohol titrating solution (0.1N), tetrabromo-mcresolsulfonphthalein indicator, by the potential difference titration obtain with in and the mg number of the potassium hydroxide of the needed hydrochloric acid equivalent of 1g sample.

＜secondary amine value 〉

For secondary amine value, be from the measured value of the total amount of secondary amine value and tertiary amine value, to deduct the measured value of tertiary amine value and the mg number with respect to the potassium hydroxide of 1g sample obtained.

＜primary amine value 〉

For primary amine value, be from the measured value of total amine value, to deduct the measured value of total amount of secondary amine value and tertiary amine value and the mg number with respect to the potassium hydroxide of 1g sample obtained.

Hydroxyl value is measured according to the B method of JIS K 1557.

In addition, water utilization has used the coulometric titration of Karl Fischer moisture gauge to measure.

Number-average molecular weight is obtained by hydroxyl value according to following formula.

Number-average molecular weight=112200/ (hydroxyl value of polyether polyols)

Each composition that uses in an embodiment is as follows.

" JEFFAMINE M-1000 "; Huntsman company system

Poly-(mol ratio of propylene oxide/oxyethane=3/19) multipolymer of a primary amine end, number-average molecular weight 1000.

" JEFFAMINE M-2070 "; Huntsman company system

Poly-(mol ratio of propylene oxide/oxyethane=10/31) multipolymer of a primary amine end, number-average molecular weight 2000.

" ETERNACOLL UH-200 "; Emerging product company of space section system

The own ester of the polymerized thylene carbonate of two primary alconol ends, number-average molecular weight 2000.

" ETERNACOLL UHC50-200 "; Emerging product company of space section system

The own ester of the polycaprolactone/polymerized thylene carbonate of two primary alconol ends (1/1 mol ratio) multipolymer, number-average molecular weight 2000.

" NIPPORAN 4009 "; Japan URETHANE company system

The polytetramethylene glycol adipic acid ester of two primary alconol ends, number-average molecular weight 1000.

" Terathane2000 "; Dupont company system

The polytetramethylene glycol of two primary alconol ends, number-average molecular weight 2000.

Embodiment 1 (polyether polyols A1)

In the stainless steel autoclave of the ingress pipe that possesses thermometer, nitrogen ingress pipe, oxyethane, temp regulating function and stirrer, drop into amino polyalkylene oxide (JEFFAMINE M-1000 (total amine equivalent=1.00m equivalent/g, primary amine containing ratio 100%), HUNTSMAN company system) 4000g (4 moles), after having carried out the nitrogen displacement, stir oxyethane 361g (8.2 moles) on one side, temperature 160 ℃ down with 1 hour it progressively fed intake on one side.And then, lower to finishing reaction in 3 hours at 160 ℃.Under the decompression under 130 ℃ the state, at 1.0KPa, the reaction solution that obtains carried out 1 hour processing, obtain polyalkylene glycol A1.Polyether polyols compd A 1 is colourless transparent liquid under 40 ℃ molten state, and moisture is 0.05%, hydroxyl value is that 93.9mgKOH/g, fusing point are that 12.5 ℃, zero pour are 25.1 ℃.According to the mensuration of total amine value, tertiary amine value, secondary amine value, primary amine value, tertiary amine content is 97.4%, secondary amine content is 1.1%, primary amine content is 1.5%.

The number-average molecular weight of the polyether polyols that obtains is 1088, the ethyleneoxide addition that obtains 2 molecules in the amino of above-mentioned amino polyalkylene oxide and the polyoxy alkylidene alcohol as tertiary amine.

Embodiment 2 (polyether polyols A2)

In the stainless steel autoclave of the ingress pipe that possesses thermometer, nitrogen ingress pipe, oxyethane, temp regulating function and stirrer, drop into amino polyalkylene oxide (JEFFAMINE M-2070 (total amine equivalent=0.48m equivalent/g, primary amine containing ratio 99.3%), HUNTSMAN company system) 4140g (2.0 moles), after having carried out the nitrogen displacement, when being stirred, oxyethane 181g (4.1 moles) with 1 hour it is progressively imported down 160 ℃ of temperature.And then, lower to finishing reaction in 3 hours at 160 ℃.Under the decompression under 130 ℃ the state, at 1.0KPa, the reaction solution that obtains carried out 1 hour processing, obtain polyalkylene glycol compounds A2.Polyether polyols A2 is at room temperature for colourless transparent liquid, moisture are 0.06%, hydroxyl value is 51.7mgKOH/g, according to the mensuration of total amine value, tertiary amine value, secondary amine value, primary amine value, tertiary amine content is 96.7%, secondary amine content is 1.3%, primary amine content is 2.0%.

The number-average molecular weight of the polyether polyols that obtains is 2171, obtain 2 molecule ethyleneoxide additions in the amino of above-mentioned amino polyalkylene oxide and as the polyoxy alkylidene of tertiary amine alcohol.

Embodiment 3 (aqueous polyurethane resin dispersion-1)

Possessing stirrer, drop into as 4 of polyisocyanates in the removable flask of the four-hole of nitrogen ingress pipe and well heater, 4 '-methylene-bis (cyclohexyl isocyanate) (trade(brand)name " Desmodur W ", Beyer Co., Ltd's system) 52.6g, polycarbonate diol (trade(brand)name " ETERNACOLL UH-200 " as the number-average molecular weight 2000 of polyvalent alcohol, emerging product company of space section system) 101.5g, the polyether polyols A1 of the 66.0g that in embodiment 1, obtains, N-Methyl pyrrolidone (Mitsubishi Chemical Ind's system) 22.0g, the dibutyltin dilaurate as catalysts (with the pure medicine of light company system) that under nitrogen atmosphere, adds trace, with reacting in 4 hours to reactivity more than 99%, obtain polyurethane prepolymer.Polyurethane prepolymer 200.0g is joined among the distilled water 390g that is keeping the vigorous stirring state lentamente, make its dispersion, the 2-methyl isophthalic acid that adds 35 % by weight, 5-pentane diamine aqueous solution 17.8g carries out the chain reaction, the dispersion that obtains is filtered by 120 purpose stainless (steel) wires, obtain aqueous polyurethane resin dispersion-1.

The solid component concentration of the aqueous polyurethane resin dispersion that obtains-1 is that the viscosity under 30.9%, 20 ℃ is 38mPss.

Under close bolt state, after 2 months, do not find the separation of resinous principle 40 ℃ of keepings, kept good dispersion state.

Embodiment 4 (aqueous polyurethane resin dispersion-2)

Possessing stirrer, in the removable flask of the four-hole of nitrogen ingress pipe and well heater, input is as 4 of polyisocyanates, 4 '-methylene-bis (cyclohexyl isocyanate) (trade(brand)name " Desmodur W ", Bayer " ETERNACOLL UHC50-200 ", emerging product company of space section system) 91.6g, the polyether polyols A1 of the 79.5g that in embodiment 1, obtains, N-Methyl pyrrolidone (Mitsubishi Chemical Ind's system) 15.0g, under nitrogen atmosphere, add trace as catalysts dibutyltin dilaurate (with the pure medicine of light company system), with reacting in 4 hours to reactivity more than 99%, obtain polyurethane prepolymer.Polyurethane prepolymer 200.0g is joined among the distilled water 387g that is keeping the vigorous stirring state lentamente, make its dispersion, the 2-methyl isophthalic acid that adds 35 % by weight, 5-pentane diamine aqueous solution 17.2g carries out the chain reaction, the dispersion that obtains is filtered by 120 purpose stainless (steel) wires, obtain aqueous polyurethane resin dispersion-2.

The solid component concentration of the aqueous polyurethane resin dispersion that obtains-2 is 32.0%, the viscosity under 20 ℃ is 48mPss.

Embodiment 5 (aqueous polyurethane resin dispersion-3)

Possessing stirrer, drop into as 4 of polyisocyanates in the removable flask of the four-hole of nitrogen ingress pipe and well heater, 4 '-methylene-bis (cyclohexyl isocyanate) (trade(brand)name " Desmodur W ", Beyer Co., Ltd's system) 67.8g, polyester glycol (trade(brand)name " NOPPORAN4009 " as the number-average molecular weight 1000 of polyvalent alcohol, Japan carbamate company system) 90.0g, the polyether polyols A1 of the 58.3g that in embodiment 1, obtains, N-Methyl pyrrolidone (Mitsubishi Chemical Ind's system) 18.8g, the dibutyltin dilaurate as catalysts (with the pure medicine of light company system) that under nitrogen atmosphere, adds trace, with reacting in 4 hours to reactivity more than 99%, obtain polyurethane prepolymer.Polyurethane prepolymer 200.0g is joined among the distilled water 376g that is keeping the vigorous stirring state lentamente, make its dispersion, the 2-methyl isophthalic acid that adds 35 % by weight, 5-pentane diamine aqueous solution 21.9g carries out the chain reaction, the dispersion that obtains is filtered by 120 purpose stainless (steel) wires, obtain aqueous polyurethane resin dispersion-3.

The solid component concentration of the aqueous polyurethane resin dispersion that obtains-3 is that the viscosity under 32.0%, 20 ℃ is 42mPss.

Embodiment 6 (aqueous polyurethane resin dispersion-4)

Possessing stirrer, drop into as 4 of polyisocyanates in the removable flask of the four-hole of nitrogen ingress pipe and well heater, 4 '-methylene-bis (cyclohexyl isocyanate) (trade(brand)name " Desmodur W ", Beyer Co., Ltd's system) 111.5g, as the polyether glycol of the number-average molecular weight 2000 of polyvalent alcohol (trade(brand)name " Terathane2000 ", Dupont company system) 250.5g, the 120.7g polyether polyols A1 that in embodiment 1, obtains, the dibutyltin dilaurate as catalysts (with the pure medicine of light company system) that under nitrogen atmosphere, adds trace, with reacting in 4 hours to reactivity more than 99%, obtain polyurethane prepolymer.Polyurethane prepolymer 440.0g is joined among the distilled water 704g that is keeping the vigorous stirring state lentamente, make its dispersion, the 2-methyl isophthalic acid that adds 35 % by weight, 5-pentane diamine aqueous solution 37.8g carries out the chain reaction, the dispersion that obtains is filtered by 120 purpose stainless (steel) wires, obtain aqueous polyurethane resin dispersion-4.

The solid component concentration of the aqueous polyurethane resin dispersion that obtains-4 is that the viscosity under 38.4%, 20 ℃ is 137mPss.

Embodiment 7 (aqueous polyurethane resin dispersion-5)

Possessing stirrer, drop into as 4 of polyisocyanates in the removable flask of the four-hole of nitrogen ingress pipe and well heater, 4 '-methylene-bis (cyclohexyl isocyanate) (trade(brand)name " Desmodur W ", Beyer Co., Ltd's system) 47.5g, polyether glycol (trade(brand)name " Terathane2000 " as the number-average molecular weight 2000 of polyvalent alcohol, Dupont company system) 101.5g, the 90.0g polyether polyols A2 that in embodiment 2, obtains, the dibutyltin dilaurate as catalysts (with the pure medicine of light company system) that under nitrogen atmosphere, adds trace, with reacting in 4 hours to reactivity more than 99%, obtain polyurethane prepolymer.Polyurethane prepolymer 110.0g is joined among the distilled water 194g that is keeping the vigorous stirring state lentamente, make its dispersion, the 2-methyl isophthalic acid that adds 35 % by weight, 5-pentane diamine aqueous solution 8.8g carries out the chain reaction, the dispersion that obtains is filtered by 120 purpose stainless (steel) wires, obtain aqueous polyurethane resin dispersion-5.

The solid component concentration of the aqueous polyurethane resin dispersion that obtains-5 is that the viscosity under 36.2%, 20 ℃ is 161mPss.

Under close bolt state, after 2 months, do not find the separation of resinous principle 40 ℃ of keepings, keeping good dispersion state.

Embodiment 8 (aqueous polyurethane resin dispersion-6)

Possessing stirrer, in the removable flask of the four-hole of nitrogen ingress pipe and well heater, input is as 4 of polyisocyanates, 4 '-methylene-bis (cyclohexyl isocyanate) (trade(brand)name Desmodur W, Beyer Co., Ltd's system) 61.6g, polycarbonate diol (trade(brand)name ETERNACOLL UH-200 as the number-average molecular weight 2000 of polyvalent alcohol, emerging product company of space section system) 133.8g, dimethylol propionic acid (Tokyo changes into system) 3.03g, the 35.0g polyether polyols A1 that in embodiment 1, obtains, N-Methyl pyrrolidone (Mitsubishi Chemical Ind's system) 25.0g, under nitrogen atmosphere, reacting liquid temperature is adjusted to 92～90 ℃, the dibutyltin dilaurate as catalysts (with the pure medicine system of light) that adds trace, with reacting in 4 hours to reactivity more than 99%, then under 75 ℃ state, add triethylamine (with the pure medicine system of light) 2.28g, obtain polyurethane prepolymer.75 ℃ the polyurethane prepolymer 200.0g that obtains is joined among the distilled water 397g that is keeping the vigorous stirring state lentamente, make its dispersion, the 2-methyl isophthalic acid that adds 35 % by weight, 5-pentane diamine aqueous solution 22.1g carries out the chain reaction, the dispersion that obtains is filtered by 120 purpose stainless (steel) wires, obtain aqueous polyurethane resin dispersion-6.

The solid component concentration of the aqueous polyurethane resin dispersion that obtains-6 is that the viscosity under 32.9%, 20 ℃ is 46mPss.

Embodiment 9 (aqueous polyurethane resin dispersion-7)

Possessing stirrer, drop into as 4 of polyisocyanates in the removable flask of the four-hole of nitrogen ingress pipe and well heater, 4 '-methylene-bis (cyclohexyl isocyanate) (trade(brand)name Desmodur W, Beyer Co., Ltd's system) 35.2g, polycarbonate esterdiol (trade(brand)name ETERNACOLL UHC50-200 as the number-average molecular weight 2000 of polyvalent alcohol, emerging product company of space section system) 76.4g, dimethylol propionic acid (Tokyo changes into system) 1.73g, the 20.0g polyether polyols A1 that in embodiment 1, obtains, N-Methyl pyrrolidone (Mitsubishi Chemical Ind's system) 14.0g, under nitrogen atmosphere, adjust reacting liquid temperature to 92～90 ℃, the dibutyltin dilaurate as catalysts (with the pure medicine system of light) that adds trace, with reacting in 4 hours to reactivity more than 99%, then under 75 ℃ state, add triethylamine (with the pure medicine system of light) 1.31g, obtain polyurethane prepolymer.75 ℃ the polyurethane prepolymer 120.0g that obtains is joined among the distilled water 203g that is keeping the vigorous stirring state lentamente, make its dispersion, the 2-methyl isophthalic acid that adds 35 % by weight, 5-pentane diamine aqueous solution 11.6g carries out the chain reaction, the dispersion that obtains is filtered by 120 purpose stainless (steel) wires, obtain aqueous polyurethane resin dispersion-7.

The solid component concentration of the aqueous polyurethane resin dispersion that obtains-7 is that the viscosity under 33.2%, 20 ℃ is 54mPss.

Embodiment 10 (aqueous polyurethane resin dispersion-8)

Possessing stirrer, drop into isophorone diisocyanate (the trade(brand)name Desmodur I as polyisocyanates in the removable flask of the four-hole of nitrogen ingress pipe and well heater, Beyer Co., Ltd's system) 36.2g, polyester glycol (trade(brand)name NOPPORAN4009 as the number-average molecular weight 1000 of polyvalent alcohol, Japan carbamate company system) 78.7g, dimethylol propionic acid (Tokyo changes into system) 1.45g, the 20.6g polyether polyols A1 that in embodiment 1, obtains, N-Methyl pyrrolidone (Mitsubishi Chemical Ind's system) 14.0g, under nitrogen atmosphere, reacting liquid temperature is adjusted to 80～88 ℃, the dibutyltin dilaurate as catalysts (with the pure medicine system of light) that adds trace, with reacting in 4 hours to reactivity more than 99%, then under 75 ℃ state, add triethylamine (with the pure medicine system of light) 1.09g, obtain polyurethane prepolymer.75 ℃ the polyurethane prepolymer 100.0g that obtains is joined among the distilled water 220g that is keeping the vigorous stirring state lentamente, make its dispersion, the 2-methyl isophthalic acid that adds 35 % by weight, 5-pentane diamine aqueous solution 9.5g carries out the chain reaction, the dispersion that obtains is passed through 120 purpose stainless (steel) wires, obtain aqueous polyurethane resin dispersion-8.

The solid component concentration of the aqueous polyurethane resin dispersion that obtains-8 is that the viscosity under 31.8%, 20 ℃ is 47mPss.

Embodiment 11 (aqueous polyurethane resin dispersion-9)

Possessing stirrer, add as 4 of polyisocyanates in the removable flask of the four-hole of nitrogen ingress pipe and well heater, 4 '-methylene-bis (cyclohexyl isocyanate) (trade(brand)name Desmodur W, Beyer Co., Ltd's system) 119.9g, polyether glycol (trade(brand)name Terathane2000 as the number-average molecular weight 2000 of polyvalent alcohol, Dupont company system) 250.5g, dimethylol propionic acid (Tokyo changes into system) 2.38g, the 120.7g polyether polyols A1 that in embodiment 1, obtains, under nitrogen atmosphere, reacting liquid temperature is adjusted to 92～90 ℃, the dibutyltin dilaurate as catalysts (with the pure medicine system of light) that adds trace, with reacting in 4 hours to reactivity more than 99%, obtain polyurethane prepolymer.75 ℃ the polyurethane prepolymer 440.0g that obtains is joined among the distilled water 704g that is keeping the vigorous stirring state lentamente, the 2-methyl isophthalic acid that adds 35 % by weight, 5-pentane diamine aqueous solution 39.8g, carry out the chain reaction, the dispersion that obtains is filtered by 120 purpose stainless (steel) wires, obtain aqueous polyurethane resin dispersion-9.

The solid component concentration of the aqueous polyurethane resin dispersion that obtains-9 is that the viscosity under 38.2%, 20 ℃ is 163mPss.

Embodiment 12 (aqueous polyurethane resin dispersion-10)

Possessing stirrer, in the removable flask of the four-hole of nitrogen ingress pipe and well heater, input is as 4 of polyisocyanates, 4 '-methylene-bis (cyclohexyl isocyanate) (trade(brand)name Desmodur W, Beyer Co., Ltd's system) 26.1g, polycarbonate esterdiol (trade(brand)name ETERNACOLL UHC50-200 as the number-average molecular weight 2000 of polyvalent alcohol, emerging product company of space section system) 60.2g, dimethylol propionic acid (Tokyo changes into system) 1.52g, the 29.0g polyether polyols A2 that in embodiment 2, obtains, under nitrogen atmosphere, reacting liquid temperature is adjusted to 92～90 ℃, the dibutyltin dilaurate as catalysts (with the pure medicine system of light) that adds trace, with reacting in 4 hours to reactivity more than 99%, obtain polyurethane prepolymer.75 ℃ the polyurethane prepolymer 100g that obtains is joined among the distilled water 220g that is keeping the vigorous stirring state lentamente, make its dispersion, the 2-methyl isophthalic acid that adds 35 % by weight, 5-pentane diamine aqueous solution 8.3g carries out the chain reaction, the dispersion that obtains is filtered by 120 purpose stainless (steel) wires, obtain aqueous polyurethane resin dispersion-10.

The solid component concentration of the aqueous polyurethane resin dispersion that obtains-10 is that the viscosity under 31.0%, 20 ℃ is 81mPss.

Utilizing the rod of 50 rods to be coated with the aqueous polyurethane resin dispersion that machine will obtain in embodiment 3～11 is coated on the plate of polycarbonate resin base material (trade(brand)name " Lupilon ", engineering plastics company of Mitsubishi system) and timber (birch material).After polycarbonate is coated with membrane sample and places an evening, 80 ℃ lower dry 20 minutes, timber is coated with membrane sample dry 1 week under 25 ℃, the environment of relative humidity 50%.

According to JIS D 0202-1988, the membrane sample that is coated with that obtains is carried out the checker belt stripping test.Utilize glass paper tape (trade(brand)name " CT24 ", NICHIBAN company system), after referring to that abdomen is sealed at film, peel off.For judgement, with the quantitaes of the piece lattice in 100 (1 2mm four directions), do not peeled off, waterborne polyurethane resin is filmed situation about not peeling off with 100/100 expression, with situation about fully peeling off with 0/100 expression.The result is as shown in table 1.

[table 1]

	Embodiment 3	Embodiment 4	Embodiment 5	Embodiment 6	Embodiment 7
						Polycarbonate	100/100	100/100	100/100	52/100	26/100
The birch material	100/100	100/100	100/100	100/100	100/100

	Embodiment 8	Embodiment 9	Embodiment 10	Embodiment 11	Embodiment 12
						Polycarbonate	100/100	100/100	100/100	97/100	100/100
The birch material	100/100	100/100	100/100	100/100	100/100

Embodiment 13 (aqueous polyurethane resin dispersion-11)

Has stirrer, drop into as 4 of polyisocyanates in the removable flask of the four-hole of nitrogen ingress pipe and well heater, 4 '-methylene-bis (cyclohexyl isocyanate) (trade(brand)name Desmodur W, Beyer Co., Ltd's system) 61.6g, polycarbonate diol (trade(brand)name ETERNACOLL UH-200 as the number-average molecular weight 2000 of polyvalent alcohol, emerging product company of space section system) 115.6g, dimethylol propionic acid (Tokyo changes into system) 4.00g, the 63.6g polyether polyols A1 that in embodiment 1, obtains, methylcarbonate (emerging product company of space section system) 60.0g, under nitrogen atmosphere, reacting liquid temperature is adjusted to 92～90 ℃, the dibutyltin dilaurate as catalysts (with the pure medicine system of light) that adds trace, with reacting in 4 hours to reactivity more than 99%, obtain polyurethane prepolymer solution.The viscosity of the polyurethane prepolymer solution that obtains under 70 ℃ is 2300mPas, can disperse in water, thereby be enough low viscous solution.75 ℃ the polyurethane prepolymer solution 261.6g that obtains is joined among the distilled water 415g that is keeping the vigorous stirring state lentamente, make its dispersion, the 2-methyl isophthalic acid that adds 35 % by weight, 5-pentane diamine aqueous solution 21.5g, carry out the chain reaction, the dispersion that obtains is filtered by 120 purpose stainless (steel) wires, obtain aqueous polyurethane resin dispersion-11.

The solid component concentration of the aqueous polyurethane resin dispersion that obtains-11 is that the viscosity under 31.3%, 20 ℃ is 21mPas.

At close bolt state, after 2 months, do not find the separation of resinous principle 40 ℃ of keepings, kept good dispersion state.

In addition, the solvent when making as polyurethane prepolymer, therefore the methylcarbonate of the right and wrong VOC material of use does not detect the VOC material substantially from the aqueous polyurethane resin dispersion that obtains.

Embodiment 14 (aqueous polyurethane resin dispersion-12)

Except using diethyl carbonate (emerging product company of space section system) to replace methylcarbonate to make the pre-polymer solution, carry out the operation identical with embodiment 13, obtain aqueous polyurethane resin dispersion-12.The viscosity of the pre-polymer solution that obtains under 70 ℃ is 2740mPas, can disperse in water, thereby be enough low viscous solution.The solid component concentration of the aqueous polyurethane resin dispersion that obtains-12 is that the viscosity under 31.3%, 20 ℃ is 23mPas.

In addition, the solvent when making as polyurethane prepolymer, therefore the methylcarbonate of the right and wrong VOC material of use, does not detect the VOC material substantially from the aqueous polyurethane resin dispersion that obtains.

Comparative example 1

Use methylcarbonate as solvent, in addition, carry out the operation identical with embodiment 13, synthetic prepolymer solution.The viscosity of pre-polymer solution under 70 ℃ is 38300mPas, lacks flowability, thereby is difficult to disperse in water.

Comparative example 2

Use is as 4 of polyisocyanates, 4 '-methylene-bis (cyclohexyl isocyanate) (trade(brand)name Desmodur W, Beyer Co., Ltd's system) 61.6g, as polycarbonate diol (trade(brand)name ETERNACOLLUH-200, emerging product company of space section system) 233.8g, dimethylol propionic acid (Tokyo changes into system) 4.00g, methylcarbonate (emerging product company of the space section system) 100.0g of the number-average molecular weight 2000 of polyvalent alcohol, with embodiment 13 synthesis of polyurethane prepolymer in the same manner.The viscosity of pre-polymer solution under 70 ℃ is 47200mPas, lacks flowability, is difficult to disperse in water.

According to embodiment 13 and embodiment 14, obtained in the mixed solvent of the carbonic ether of non-VOC material and water, all can stably keeping the aqueous polyurethane resin dispersion of dispersed body.

Claims (according to the modification of the 19th of treaty)

1. (after the revisal) a kind of aqueous polyurethane resin dispersion is scattered in the water-medium urethane resin and forms, described urethane resin be make at least the expression of polyisocyanates and general formula (1) the polyether polyols reaction and,

In the formula,

At this, R ¹≠ R ², R ³≠ R ⁴, R ⁵≠ R ⁶,

X3, Y3 represent respectively 0～135 number,

X1 and Y1 can be 0,

X2 and Y2 are not 0 simultaneously,

X3 and Y3 are not 0 simultaneously,

Can be block copolymerization polymer chain, random copolymerization polymer chain or homopolymer chain in [].

2. (deletion)

3. (deletion)

4. (deletion)

5. (deletion)

6. (deletion)

7. (deletion)

8. (deletion)

9. (deletion)

10. (after the revisal) aqueous polyurethane resin dispersion according to claim 1, wherein said urethane resin further makes the polyol reaction that contains acidic-group obtain.

(11. after the revisal) aqueous polyurethane resin dispersion according to claim 10, the wherein said acidic-group that contains the polyvalent alcohol of acidic-group is neutralized by basic cpd.

(12. after the revisal) according to claim 1, each described aqueous polyurethane resin dispersion in 10～11, wherein said urethane resin further makes except polyether polyols and other polyol reactions of containing the polyvalent alcohol of acidic-group and obtains.

(13. after the revisal) according to claim 1, each described aqueous polyurethane resin dispersion in 10～12, wherein said urethane resin further makes the chain extension agent reaction and obtains.

(14. deletion).

(15. after the revisal) according to claim 1,10～13 described aqueous polyurethane resin dispersions, wherein, water-medium contains carbonic ether and water.

(16. after the revisal) aqueous polyurethane resin dispersion according to claim 15, wherein, carbonic ether be selected from methylcarbonate, diethyl carbonate and the Methyl ethyl carbonate more than a kind.

(17. after the revisal) a kind of coating agent, it contains each described aqueous polyurethane resin dispersion in the claim 1,10～13,15～16.

The manufacture method of (18. after the revisal) a kind of aqueous polyurethane resin dispersion, it has:

Obtain the operation of polyurethane prepolymer, in containing the organic solvent of carbonic ether, at least make the following substances reaction, thereby obtain polyurethane prepolymer, described material is: the represented polyether polyols of polyisocyanates, general formula (1), the polyvalent alcohol that contains acidic-group that adds as required, add as required except polyether polyols and contain other polyvalent alcohol the polyvalent alcohol of acidic-group;

Make polyurethane prepolymer be dispersed in operation in the water-medium; And

Make the operation of polyurethane prepolymer and chain extension agent reaction,

In the formula,

At this, R ¹≠ R ², R ³≠ R ⁴, R ⁵≠ R ⁶,

X3, Y3 represent respectively 0～135 number,

X1 and Y1 can be 0,

X2 and Y2 are not 0 simultaneously,

X3 and Y3 are not 0 simultaneously,

19. the manufacture method of aqueous polyurethane resin dispersion according to claim 18 after the operation that makes the reaction of polyurethane prepolymer and chain extension agent, has the operation that the organic solvent that will contain carbonic ether heats up in a steamer.

Claims

1. the polyether polyols of a general formula (1) expression,

In the formula,

At this, R ¹≠ R ², R ³≠ R ⁴, R ⁵≠ R ⁶,

X3, Y3 represent respectively 0～135 number,

X1 and Y1 can be 0,

X2 and Y2 are not 0 simultaneously,

X3 and Y3 are not 0 simultaneously,

2. polyether polyols according to claim 1, it is to make to have 1 NH in 1 molecule ₂The amino polyalkylene oxide of base and the reaction of one or more oxiranes obtain.

3. polyether polyols according to claim 2, wherein, the epoxy alkane unit of amino polyalkylene oxide contains ethylene oxide unit.

4. each described polyether polyols according to claim 1～3, wherein, polyether polyols has ethylene oxide unit and/or propylene oxide units as repeating unit.

5. each described polyether polyols according to claim 1～4, wherein, R ¹O, R ²O, R ³O, R ⁴O, R ⁵O, R ⁶Among the O at least one is oxyethane or propylene oxide.

6. polyether polyols according to claim 5, wherein, R ¹O, R ²O, R ³O, R ⁴O, R ⁵O, R ⁶Among the O at least one is oxyethane.

7. each described polyether polyols according to claim 1～6, its number-average molecular weight is 250～6000.

8. each described polyether polyols according to claim 1～7, it has 1 alkoxyl group end and 2 C-terminals in 1 molecule.

9. urethane resin, it makes at least in polyisocyanates and the claim 1～8 each described polyether polyols reaction and obtains.

10. urethane resin according to claim 9, it further makes the polyol reaction that contains acidic-group obtain.

11. urethane resin according to claim 10, wherein, the acidic-group that contains the polyvalent alcohol of acidic-group is neutralized by basic cpd.

12. each described urethane resin according to claim 9～11, it further makes except polyether polyols and other polyol reactions of containing the polyvalent alcohol of acidic-group and obtains.

13. each described urethane resin according to claim 9～12, it further makes the chain extension agent reaction and obtains.

14. an aqueous polyurethane resin dispersion, it is dispersed in each described urethane resin in the claim 9～13 in the water-medium and obtains.

15. aqueous polyurethane resin dispersion according to claim 14, wherein, water-medium contains carbonic ether and water.

16. according to claim 14 or 15 described aqueous polyurethane resin dispersions, wherein, carbonic ether be selected from methylcarbonate, diethyl carbonate and the Methyl ethyl carbonate more than a kind.

17. a coating agent, it contains each described aqueous polyurethane resin dispersion in the claim 14～16.

18. the manufacture method of an aqueous polyurethane resin dispersion, it has:

Obtain the operation of polyurethane prepolymer, in containing the organic solvent of carbonic ether, at least make the following substances reaction, thereby obtain polyurethane prepolymer, described material is: each described polyether polyols in polyisocyanates, the claim 1～8, the polyvalent alcohol that contains acidic-group that adds as required, add as required except polyether polyols and contain other polyvalent alcohol the polyvalent alcohol of acidic-group;

Make polyurethane prepolymer be dispersed in operation in the water-medium; And