CN107011495A

CN107011495A - aqueous polyurethane dispersion

Info

Publication number: CN107011495A
Application number: CN201610866190.4A
Authority: CN
Inventors: 增渕徹夫; 上野英三郎
Original assignee: Asahi Kasei Kogyo KK
Current assignee: Asahi Kasei Corp
Priority date: 2015-10-07
Filing date: 2016-09-29
Publication date: 2017-08-04
Anticipated expiration: 2036-09-29
Also published as: CN107011495B; JP6663199B2; JP2017071684A

Abstract

It is an object of the present invention to provide can be formed without using ultraviolet lamp, hardness of film is excellent and soft, film with the sense of touch as natural leather soft-feel coating composition.The aqueous polyurethane dispersion of the present invention includes water-dispersible polyurethane and water, and the water-dispersible polyurethane is the reaction product of PCDL and (c) containing carboxyl and/or the polyalcohol of sulfo group or its salt of the organic polyisocyanate compound containing the NCO of more than 2, (b) with specific structure in (a) 1 molecule.

Description

Aqueous polyurethane dispersion

Technical field

Soft-feel coating composition the present invention relates to aqueous polyurethane dispersion and containing the aqueous polyurethane dispersion.

Background technology

In the past, polyurethane resin was used for synthetic leather, artificial leather, bonding agent, furniture coating, car paint etc. extensively Field, using polyethers, polyester be used as can with isocyanates react polyol component.However, in recent years, for heat resistance, The requirement of weatherability, hydrolytic resistance, oil resistivity, chemical proofing, low-temperature pliability etc. is being improved, and then soft for sense of touch Soft, the soft-feel coating as natural leather requirement is being improved always.In addition, from the requirement tackled for environment, it is right Improved always in the expectation of aqueous polyurethane.

It is used as the method for solving these problems, it is proposed that heat resistance, weatherability, hydrolytic resistance, oil resistivity, chemical-resistant resistance The excellent aqueous polyurethane for having used various PCDLs of property.

Proposed in patent document 1 comprising by 2- methyl isophthalic acids, the aqueous polyurethane of the PCDL of 3 propane diols formation Composition.The aqueous polyurethane composition can be used for the things such as chemical proofing, hydrolytic resistance, weatherability, flexibility, adaptation The excellent coating of sexual balance, smears, bonding agent, adhesive etc..The PCDL formed by 2- methyl-1,3-propanediols Compared to the conventional PCDL by the formation of 1,6- hexylene glycols, the crystallinity under normal temperature is low, therefore flexibility is excellent.And And, in PCDL, the concentration of carbonate group is high, therefore chemical proofing, excellent wear resistance.

Propose to have used 1,5- pentanediols and the PCDL of 1,6-HD copolymerization in patent document 2 Aqueous polyurethane dispersion.1,5-PD and 1, the PCDL of 6- hexylene glycol copolymerization are had amorphism by this, Therefore flexibility is excellent, and glass transition temperature is relatively low, therefore also improves low-temperature characteristics.

Proposed in patent document 3 (methyl) acrylate with isocyanates and containing hydroxyl to make 1,5- pentanediols and Aqueous dispersion that the makrolon two of 1,6-HD copolymerization is modified, modified polycarbonate glycol.The modification gathers The composition of the aqueous dispersion of carbonate diol is solidified by polymerization initiator with ultraviolet, so as to improve conduct Chemical proofing, the abrasion performance of above-mentioned problem.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2008-37987 publications

Patent document 2：Japanese Unexamined Patent Publication 2008-303284 publications

Patent document 3：Japanese Unexamined Patent Publication 2013-82863 publications

The content of the invention

Problems to be solved by the invention

On the other hand, the PCDL disclosed in patent document 1 has methyl, therefore transport properties of molecules in side chain Difference, flexibility is insufficient, and glass transition temperature is also uprised, therefore low-temperature characteristics can also have problem.For in patent document 2 The concentration of carbonate group in disclosed PCDL, PCDL is less than by 2- methyl isophthalic acids, and ammediol is formed PCDL, therefore the reduction of chemical proofing, abrasion performance can turn into problem.Changing disclosed in patent document 3 The composition of the aqueous dispersion of property PCDL occasionally there are in order to make solidify and need ultraviolet lamp, can The problem that the purposes used is limited.

Present invention aims at there is provided that can be formed without using ultraviolet lamp, hardness of film is excellent and soft, have Just like the soft-feel coating composition of the film of sense of touch as natural leather.

The solution used to solve the problem

As a result the present inventor etc. has found, by using by the makrolon with specific structure by furtheing investigate repeatedly The aqueous polyurethane dispersion that glycol is obtained, can obtain it is soft, with the sense of touch as natural leather and oil resistivity, resistance to The water system soft-feel coating composition of the physical property balancing good such as abrasivity, low-temperature characteristics, so as to complete the present invention.

That is, the present invention includes following proposal.

[1]

A kind of aqueous polyurethane dispersion, it includes water-dispersible polyurethane and water, and the water-dispersible polyurethane is (a) Organic polyisocyanate compound, (b) PCDL and (c) containing the NCO of more than 2 in 1 molecule Reaction product containing carboxyl and/or the polyalcohol of sulfo group or its salt,

Foregoing (b) PCDL is with the repeat unit and the makrolon of terminal hydroxyl shown in following formula (1) The construction unit shown in following formula (2) comprising 20 moles of more than % in glycol, the construction unit shown in formula (1).

(in formula, R₁Represent the aliphatic hydrocarbon or clicyclic hydrocarbon of the divalence of carbon number 2~20.)

[2]

Aqueous polyurethane dispersion according to [1], wherein, foregoing (b) PCDL is shown in previously described formula (1) Construction unit in include construction unit shown in the previously described formula (2) for being more than 90 moles of %.

[3]

Aqueous polyurethane dispersion according to [2], wherein, the end primary hydroxyl of foregoing (b) PCDL (OH) ratio is more than 95% and less than 99.5%, and the number-average molecular weight of foregoing (b) PCDL is 300~5000.

[4]

Aqueous polyurethane dispersion according to [2] or [3], wherein, foregoing (a) organic polyisocyanate compound is Aliphatic organic diisocyanate compound and/or alicyclic organic diisocyanate compound.

[5]

A kind of water system soft-feel coating composition, it contains the aqueous polyurethane dispersion any one of [2]~[4].

[6]

Aqueous polyurethane dispersion according to [1], wherein, foregoing (b) PCDL is shown in previously described formula (1) Construction unit in construction unit shown in the following formula (2) comprising 20 moles of more than % and 90 mole of below %.

[7]

Aqueous polyurethane dispersion according to [6], wherein, the end primary hydroxyl of foregoing (b) PCDL (OH) ratio is more than 95% and less than 99.5%, and the number-average molecular weight of foregoing (b) PCDL is 300~5000.

[8]

Aqueous polyurethane dispersion according to [6] or [7], wherein, foregoing (a) organic polyisocyanate compound is Aliphatic organic diisocyanate compound and/or alicyclic organic diisocyanate compound.

[9]

A kind of water system soft-feel coating composition, it contains the aqueous polyurethane dispersion any one of [6]~[8].

The effect of invention

, can be without using by using the obtained water system soft-feel coating composition of aqueous polyurethane dispersion by the present invention There is provided that hardness of film is excellent and soft, film with the sense of touch as natural leather ultraviolet lamp.

Embodiment

Below, the mode (below, referred to as " present embodiment ") for implementing the present invention is explained.Need It is bright, the invention is not restricted to implementation below, it can carry out various modifications to implement in the range of its purport.

The aqueous polyurethane dispersion of present embodiment includes water-dispersible polyurethane and water, the water-dispersible polyurethane Be the organic polyisocyanate compound containing the NCO of more than 2 in (a) 1 molecule, (b) PCDL, with And the reaction product of (c) containing carboxyl and/or the polyalcohol of sulfo group or its salt, foregoing (b) PCDL is with following 20 moles of % are included in the PCDL of repeat unit and terminal hydroxyl shown in formula (1), the construction unit shown in formula (1) Construction unit shown in following formula (2) above.

On the first scheme of present embodiment, preferably above-mentioned (b) PCDL is in the structure shown in above-mentioned formula (1) The construction unit shown in the above-mentioned formula (2) for being more than 90 moles of % is included in unit.

On the alternative plan of present embodiment, preferably above-mentioned (b) PCDL is in the structure shown in above-mentioned formula (1) The construction unit shown in above-mentioned formula (2) comprising 20 moles of more than % and 90 mole of below % in unit.

<(a) organic polyisocyanate compound>

As (a) organic polyisocyanate compound for present embodiment, as long as contain more than 2 in 1 molecule The organic polyisocyanate compound of NCO be just not particularly limited.It is used as (a) organic polyisocyanate compound Example, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, cyclohexane diisocyanate, toluene two can be enumerated different Cyanate, hexamethylene diisocyanate (HDI), trimethylhexane diisocyanate, 1,5- naphthalene diisocyanates, xyxylene Diisocyanate, 2,6- diisocyanate methyl caproate, IPDI (IPDI), hexahydrotoluene -2,4- two Aromatic series, the fat such as isocyanates or hexahydrotoluene -2,6- diisocyanate, 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate) Fat race, alicyclic ring family organic diisocyanate；Or their biuret body, isocyanuric acid ester body etc. is polyfunctional contains isocyanic acid The polymer of ester group；Or these single isocyanates or their mixture.

Especially from the viewpoint of weatherability, (a) organic polyisocyanate compound is preferably aliphatic and/or alicyclic Organic diisocyanate compound, specifically, more preferably HDI, IPDI, dodecane diisocyanate, the isocyanide of hexamethylene two The aliphatic such as acid esters, dicyclohexyl methyl hydride diisocyanate, alicyclic diisocyanate；Or the mixture of these isocyanates.

<(b) PCDL>

(b) PCDL for being used to manufacture aqueous polyurethane dispersion of the first scheme of present embodiment has The repeat unit and terminal hydroxyl shown in formula (1) are stated, is included in the construction unit shown in above-mentioned formula (1) and is more than 90 moles of %'s Construction unit shown in above-mentioned formula (2), preferably comprises 95 moles of more than %, more preferably comprising 98 moles of more than %.

Above-mentioned (b) PCDL can for example be derived by the dihydric alcohol based on 1,3- propane diols and carbonate products Out.

For the water system soft-feel coating composition obtained by aqueous polyurethane dispersion of the first scheme of present embodiment Film performance, because above-mentioned (b) PCDL is noncrystalline, therefore with the excellent feature of flexibility.Using similar During the straight-chain aliphatic PCDLs such as BDO, 1, the 6- hexylene glycols of structure, for the film of gained aqueous coating Performance, these straight-chain aliphatic PCDLs are crystallinity, therefore flexibility is poor.In addition, using by being chained with branch The 2- methyl isophthalic acids of structure, during the Aliphatic Polycarbonatediols that ammediol is derived, for the film performance of gained aqueous coating, Because pendant methyl hinders molecular motion, cause that flexibility is poor, glass transition temperature is also uprised, low-temperature pliability it is impaired.

(b) PCDL for being used to manufacture aqueous polyurethane dispersion of the alternative plan of present embodiment has State in the repeat unit and terminal hydroxyl shown in formula (1), the construction unit shown in formula (1) comprising 20 moles of more than % and 90 rub Construction unit shown in your below % above-mentioned formula (2), preferably 30 moles more than % and 80 mole of below %, more preferably 40 Mole more than % and 70 mole of below %.

It is 90 moles of below % by the ratio, can fully obtains copolymerization effect (by making 2 kinds of constituted alkylenes Base irregular alignment, intermolecular carbonate group becomes irregular each other, interaction reduction), contain gained aqueous polyurethane point The flexibility of the water borne soft-feel coating composition of granular media is improved.It is amorphous by 1,3-PD by for 20 moles of more than % The ratio of the construction unit of formation becomes abundant, the water borne soft-feel coating composition containing gained aqueous polyurethane dispersion it is soft It is soft to improve.

Dihydric alcohol shown in following formula (3) and following formula (4) and carbonic ester can be used for by above-mentioned PCDL Raw material, is synthesized by ester exchange.

HO-R₁-OH (3)

HO-CH₂-CH₂-CH₂-OH (4)

As the specific example of the dihydric alcohol shown in the above-mentioned formula (3) used in the alternative plan of present embodiment, except Beyond 1,3-PD shown in above-mentioned formula (4), ethylene glycol, 2- methyl isophthalic acids can also be enumerated, ammediol, BDO, 1,5- pentanediols, 1,6-HD, 1,7- heptandiols, 1,8- ethohexadiols, 1,9- nonanediols, 1,10- decanediols, 2- methyl isophthalic acids, 8- ethohexadiols, neopentyl glycol, 2- isopropyl -1,4- butanediols, 2- ethyls -1,6-HD, 3- methyl isophthalic acids, 5- pentanediols, 2, 4- dimethyl -1,5- pentanediols, 2,4- diethyl -1,5- pentanediols, 1,3- cyclohexanediols, 1,4- cyclohexanediols, 1,4- hexamethylenes Double (4- hydroxy-cyclohexyls) propane of alkane dimethanol, 2- etc..In addition to 1,3-PD, the dihydric alcohol shown in formula (3) can be only It is used singly, or in combination of two or more kinds.Wherein, the straight-chain alkyl-sub glycol of carbon number 2~10 is preferably used.Wherein, more Preferably use 1,4- butanediols, 1,5- pentanediols, 1,6-HD.

End primary hydroxyl (OH) ratio of (b) PCDL used in present embodiment is preferably more than 95.0% And less than 99.5%, more preferably more than 97.0% and less than 99.0%.In present embodiment, the end of (b) PCDL End primary hydroxyl (OH) ratio refers to following value：PCDL (70g~100g) is following in below 0.4kPa pressure Stirring side is heated at a temperature of 160 DEG C~200 DEG C, thus obtains about 1~2 matter equivalent to the PCDL Cut, i.e. about 1g (0.7~2g) cut at initial stage of % amount are measured, is returned using about 100g (95~105g) ethanol as solvent The cut is received, the value that gas-chromatography (GC) is analyzed and obtains the peak area of chromatogram is implemented to the solution of recovery, by the chromatogram The value that the value of the peak area of figure is calculated according to following formula (5).

Terminal primary OH ratios (%)=B ÷ A × 100 (5)

A：The summation of the peak area of alcohols (in addition to ethanol) comprising dihydric alcohol

B：Two ends are the summation of the peak area of the dihydric alcohol of primary OH bases

Primary OH ends ratio is the ratio shared by primary OH bases in total end group of PCDL.That is, as above institute State, can obtain as follows：When PCDL is heated into 160 DEG C~200 DEG C of temperature under below 0.4kPa pressure, The end section of PCDL is departed from the form of alcohols, evaporated, and is obtained as cut.

(b) end primary hydroxyl (OH) the base ratio of PCDL is more than 95.0%, so as to can be easy in the short time It is interior to improve molecular weight to desired value, it is possible to increase productivity ratio.In addition, the water system soft feeling containing gained aqueous polyurethane dispersion The case hardness of coating composition, abrasion performance, chemical proofing tend to be more excellent.(b) end of PCDL Primary hydroxyl (OH) base ratio is less than 99.5%, so as to further reduce the dispersible granule of gained aqueous polyurethane dispersion Footpath, can make the storage-stable of aqueous polyurethane dispersion better, be preferred.In addition, containing the poly- ammonia of gained water system The outward appearance of the water system soft-feel coating composition of ester dispersion, coating strength, abrasion performance tend to be more excellent.

To end primary hydroxyl (OH) the base rate control of (b) PCDL is not special in the method for aforementioned range Limitation, but such as can enumerate following method：In the polymerization of (b) PCDL or polymerization terminate after, addition rule Quantitative monohydric alcohol, is heated；Binary is added in the dihydric alcohol of the polymer raw of (b) PCDL microly Secondary alcohol.

In present embodiment, (b) PCDL is, for example, by Schell works, Polymer Review volumes 9, the Various methods described in page 9~20 (1964) are come the PCDL that synthesizes.

(b) PCDL for the first scheme of present embodiment is, for example, the straight chain synthesized by 1,3- propane diols Aliphatic Polycarbonatediols, in the range of its feature is not hindered, can also contain other low molecular weight diol conducts Copolymer composition.Specifically, as workable other dihydric alcohols, for example, ethylene glycol, 1,2-PD, 1,2- can be enumerated Butanediol, 1,3 butylene glycol, 1,4- butanediols, 2- methyl-1,3-propanediols, neopentyl glycol, 2,3- butanediols, 1,5- penta 2 Alcohol, 2- methyl isophthalic acids, 5- pentanediols, 1,6-HD, 2,5-HD, 1,7- heptandiols, 1,8- ethohexadiols, 2- methyl isophthalic acids, 8- Ethohexadiol, 1,9- nonanediols, 1,10- decanediols, 1,11- undecanes, 1,12- dodecanediols, 1,4- cyclohexanediols, 1, 4- cyclohexanedimethanols etc..The ratio for the dihydric alcohol that can contain as these copolymer compositions is with comprising the total of 1,3- propane diols Shared ratiometer in monomer dihydric alcohol, preferably less than 10 mass %, more preferably less than 8 mass %, more preferably Less than 6 mass %.

Number-average molecular weight for (b) PCDL of present embodiment is preferably 300~5000, more preferably 500~4000, more preferably 1000~3000.It is more than 300 by the number-average molecular weight of (b) PCDL, has The flexibility of film becomes more good, the more excellent tendency of soft feeling.In addition, equal by the number of (b) PCDL Molecular weight is less than 5000, when the end group of manufacture high polymer main chain is the polyurethane of OH bases, the reaction with isocyanates Accelerate, productivity ratio becomes good, and have the viscosity that can reduce gained water-dispersible polyurethane, it is easier to disperse in water Tendency.

To the number-average molecular weight control of (b) PCDL is not particularly limited in the method for aforementioned range, for example The control when (b) PCDL polymerize, which can be enumerated, will distill method of amount of glycol monomer of removal etc..

In present embodiment, as (b) PCDL, also comprising by using dihydric alcohol and a small amount of 1 point of use There is compound such as trimethylolethane, trimethylolpropane, hexanetriol, pentaerythrite, the glycerine of more than 3 hydroxyls in son Deng so as to by the average hydroxyl number in a multiple functionalized molecule be more than 2 polycarbonate polyol.

<(c) polyalcohol or its salt>

(c) for present embodiment is in order at containing carboxyl and/or the polyalcohol of sulfo group or its salt gathers water dispersible Urethane occur in water self-emulsifying and assign aqueous polyurethane dispersion dispersion stabilization purpose and import carboxylic acid ester groups or Composition used in sulfonate group.Carboxylic polyalcohol is not particularly limited, for example, can enumerate 2,2- dihydroxymethyls third Sour (DMPA), 2,2- dimethylolpropionic acids, 2,2- dihydroxymethyls enanthic acid, 2,2- dihydroxymethyl octanoic acids etc..In addition, to containing sulfo group Polyalcohol is not particularly limited, for example, can enumerate sulfonic acid glycol { 3- (2,3- dihydroxy propoxyl group) -1- propane sulfonic acids } and ammonia Base sulfonic acid glycol { double (2- hydroxyalkyls (the hydroxylkyl)) sulfamic acids of N, N- } and its epoxide adduct etc..To these The salt of polyalcohol containing carboxyl and/or sulfo group is not particularly limited, for example, can enumerate ammonium salt, amine salt [the primary of carbon number 1~12 Amine (unary primary amine, such as methylamine, ethamine, propylamine and octylame) salt, unitary secondary amine (dimethylamine, diethylamine and dibutyl Amine) salt, the unitary tertiary amine (fat such as trimethylamine, triethylamine, triethanolamine, N methyldiethanol amine and N, N- dimethylethanolamine Fat race unitary tertiary amine；The hetero ring type unitary tertiary amine such as N- methyl piperidines and N-methylmorpholine；Benzyl dimethylamine, α-methylbenzyl diformazan Amine；And the unitary tertiary amine containing aromatic ring such as accelerine) salt], alkali metal (sodium, potassium and lithium cation) salt and wherein Of more than two kinds be applied in combination.

Amine salt is preferably in salt, it is further preferred that aliphatic unitary tertiary ammonium salt, particularly preferably triethylamine salt.

Should (c) polyalcohol be the polyalcohol containing carboxyl and/or sulfo group and during non-salt, can be used nertralizer by carboxyl and/ Or sulfo group is neutralized, so that carboxylic acid ester groups and/or sulfonate group is made.

As nertralizer, the alkali compounds for forming the foregoing cation enumerated as counter ion counterionsl gegenions can be enumerated. For example, ammonia, amine [primary amine (unary primary amine, such as methylamine, ethamine, propylamine and octylame), the unitary of carbon number 1~12 can be enumerated Secondary amine (dimethylamine, diethylamine and dibutylamine), unitary tertiary amine (trimethylamine, triethylamine, triethanolamine, N- methyl diethanols The aliphatic unitary tertiary amine such as amine and N, N- dimethylethanolamine；The hetero ring type unitary uncle such as N- methyl piperidines and N-methylmorpholine Amine；Benzyl dimethylamine, α-methylbenzyl dimethylamine；And the unitary tertiary amine containing aromatic ring such as accelerine)], alkali metal (sodium, potassium and lithium cation), alkali metal hydroxide and two or more of them be applied in combination.

Wherein it is preferred that amine, it is further preferred that aliphatic unitary tertiary amine, particularly preferably triethylamine.

(c) the preferred carboxyl of usage amount and/or sulfo group containing carboxyl and/or the polyalcohol of sulfo group or its salt are relative to moisture Dissipate the amount that property polyurethane is 0.01~10 mass %.Carboxyl and/or sulfo group relative to water-dispersible polyurethane ratio more preferably For 0.1~7 mass %, more preferably 0.5~5 mass %.It is more than 0.01 mass %, breast by carboxyl and/or sulfo group Liquid stability tends to be more excellent.In addition, tending to be more excellent by the water resistance for below 10 mass %, gained film.

Alternatively, it is also possible to by suitable surfactant for example with higher fatty acids, resin acid, acid fatty alcohol, sulfuric acid Ester, sulfonic acid higher alkyl esters, alkyl aryl sulfonic acid ester, sulfonated castor oil, esters of sulfosuccinic acids etc. are the anionic property table of representative Face activating agent or using the known reaction product of oxirane and long-chain fatty alcohol or oxirane and phenols as the non-of representative Ionic surfactant etc. is applied in combination to keep emulsion stability.Wherein, surfactant preferably is nonionic table Face activating agent.

Manufacture method to the aqueous polyurethane dispersion of present embodiment is not particularly limited, for example, can enumerate as follows Method.The organic solvent of the group containing reactive hydrogen is not included (for example, acetone, MEK, tetrahydrofuran, N, N- in intramolecular Dimethylformamide etc.) in the presence of or it is non-in the presence of, the organic many of the NCO of more than 2 will be contained in (a) 1 molecule Isocyanates, (b) PCDL and (c) are containing carboxyl and/or the polyalcohol of sulfo group or its salt with (NCO bases/OH yls) Equivalent proportion is preferably 0.5~1.5 scope, more preferably 0.8~1.2 scope, more preferably 0.9~1.1 scope Ground carries out urethane reaction and synthesis of polyurethane by one-step method or multistep processes, as needed with nertralizer by the poly- ammonia Ester is neutralized, and then carries out strong mixing to the obtained reaction solution, water is now added dropwise, after completion of dropwise addition, solvent is removed as needed, So as to obtain aqueous polyurethane dispersion.

It is allowed to scattered in water alternatively, it is also possible to which obtained above-mentioned reaction solution is added while stirring, then as needed Solvent is removed to obtain aqueous polyurethane dispersion.

By making (NCO bases/OH yls) equivalent proportion be more than 0.5, the molecule quantitative change of gained polyurethane can be made big, tend to energy More stable aqueous polyurethane dispersion is accessed, and then is combined using aqueous polyurethane dispersion as the soft-feel coating of constituent Painting film strength, the flexibility that thing is formed tend to be more excellent.In addition, by with (NCO bases/OH yls) equivalent proportion be 1.5 with Under, it can similarly make the molecule quantitative change of gained polyurethane big, tend to that more stable aqueous polyurethane dispersion can be obtained, enter And painting film strength, the flexibility formed using aqueous polyurethane dispersion by the water system soft-feel coating composition of constituent becomes In more excellent.

In addition, the manufacture method of the aqueous polyurethane dispersion as present embodiment, can also be in advance by (a) 1 molecule In the organic multiple isocyanate containing the NCO of more than 2, (b) PCDL and (c) containing carboxyl and/ Or the polyalcohol of sulfo group or its salt, the synthetic prepolymer under conditions of isocyanates excess, the prepolymer is dispersed in water it Afterwards, add chain extender and aqueous polyurethane dispersion is made.

Chain extender is not particularly limited, it is short such as can enumerate water, ethylene glycol, 1,3-PD, BDO Chain dihydric alcohol；Hydrazine, ethylenediamine, diethyl triamine, trien, tetren, penten, propane diamine, Many amines such as hexamethylene diamine, cyclohexanediamine.The addition of chain extender is commonly angled relative to the isocyanide of carbamate prepolymer 1 mole of perester radical is 0~1.2 mole, preferably 0.1~0.6 mole.

During the aqueous polyurethane dispersion for manufacturing present embodiment, known amino first can be used as needed Esterification catalysts.As urethane catalysts, amines catalyst, such as triethylamine, N- can be enumerated Ethyl morpholine, triethylenediamine etc.；Tin series catalysts, such as dibutyl tin laurate, tin dilaurate dioctyl tin and Tin octoate；Titanium series catalyst, such as butyl titanate.

The solid constituent of the aqueous polyurethane dispersion of present embodiment is preferably 10~70 mass %, more preferably 20~ 60 mass %.

In addition, the particle diameter of the polyurethane of the aqueous polyurethane dispersion of present embodiment is preferably below 500nm, more preferably For below 200nm, more preferably below 150nm.It is below 500nm by the particle diameter of polyurethane, contains aqueous polyurethane The outward appearance of the film of the water system soft-feel coating composition of dispersion, intensity, abrasion performance tend to become more excellent, are preferred 's.

The water system soft-feel coating composition of present embodiment contains above-mentioned aqueous polyurethane dispersion.

In the water system soft-feel coating composition of present embodiment, the content of above-mentioned aqueous polyurethane dispersion is preferably 10~ 98 mass %, more preferably 20~95 mass %, more preferably 30~90 mass %.

According to various uses, filler, fire retardant, dye can be added in the water system soft-feel coating composition of present embodiment Material, organic pigment or inorganic pigment, releasing agent, fluidity regulator, plasticizer, antioxidant, ultra-violet absorber, light are stable Agent, defoamer, levelling agent, colouring agent, solvent etc..

Filler, pigment are not particularly limited, can for example use weave cotton cloth, glass fibre, carbon fiber, polyamide it is fine Dimension, mica, kaolin, bentonite, metal powder, AZOpigments, carbon black, clay, silica, talcum, gypsum, aqua oxidation The usually used material such as aluminium, barium carbonate, resin particle.Wherein, to obtain the soft sense of touch as the purpose, preferably set The particulate of fat particulate, more preferably polyurethane.

Releasing agent, fluidity regulator, levelling agent are not particularly limited, for example, can be used such as polysiloxanes, airsetting Polysiloxanes etc. as glue, wax, stearate, BYK-331 (BYK chemical Co., Ltd. system).

As the additive for present embodiment, preferably at least using antioxidant, light stabilizer and thermally-stabilised Agent.These antioxidants are not particularly limited, for example, phosphoric acid, the aliphatic of phosphorous acid, aromatic series or alkyl can be used to take For aromatic ester, hypophosphorous acid derivative；Benzene sulfonic acid, phenyl-phosphinic acid, diphenyl phosphonic acid, polyphosphonates, dialkyl group pentaerythrite two The phosphorus compounds such as phosphite ester, dialkyl bisphenol A diphosphites；Phenol system derivative especially hindered phenol compound, thioether system, Two thiosalt systems；The compound of the sulfur-bearings such as mercaptobenzimidazole system, thiocarbanilide system, thiodipropionate；Maleic acid tin, The tin based compound such as Dibutyltin oxide.They can be used alone, and can also combine two or more and use.

The coating process of the water system soft-feel coating composition of present embodiment is not particularly limited, can be exemplified in water system After mixing each additive component in dispersions of polyurethanes, the method being coated with sprayer, roller, brush etc. on base material.

Embodiment

Below, the present invention is described in more detail using embodiment etc., but the present invention at all not because of these examples by Limit.The evaluation of analysis method and Physical properties of coating film in following examples and comparative example is implemented according to tests below method.

1) number-average molecular weight of PCDL

Hydroxyl value is determined according to JIS K1557-1, calculated using following formula (6).

Number-average molecular weight=2/ (OH value × 10^-3/56.1) (6)

2) the terminal primary OH ratios of PCDL

The terminal primary OH ratios in PCDL are determined as follows.First, 70g~100g makrolon two is measured Alcohol is into 300ml eggplant type flask.Using the Rotary Evaporators for being connected to cut recovery recovery ball, by foregoing eggplant type flask PCDL heated and be stirred under below 0.4kPa pressure, in about 180 DEG C of heating bath so that About 1~2 mass % cut equivalent to the PCDL, i.e. about 1g (0.7~2g) initial stage is obtained in recovery ball to evaporate Point.In the ethanol that obtained cut is dissolved in about 100g (95~105g), reclaim as a solution.The solution of recovery is entered Promoting the circulation of qi analysis of hplc (hereinafter also referred to " GC analyses "), according to following formula (5) by the value meter of the obtained peak area of chromatogram Calculate the end OH base ratios in PCDL.It should be noted that GC analyses are to use to be provided with 0.25 μm of 30m, thickness The gas chromatograph 6890 (U.S.'s Hewlett-Packard Company systems) of DB-WAX (U.S.'s J＆W company systems) post, conduct What the flame ionization ditector (FID) of detector was carried out.The heating curve of post is set to be warming up to 10 DEG C/min from 60 DEG C After 250 DEG C, the curve of 15 minutes is kept at such a temperature.The identification at each peak in GC analyses is to use following GC-MS devices Carry out.GC devices use the 6890 (U.S. Hewlett-Packard for being provided with DB-WAX (U.S.'s J＆W company systems) post Company systems).In GC devices, 220 DEG C are warming up to for 10 DEG C/min from 40 DEG C of temperature at initial stage with programming rate.MS devices are used Auto-massSUN (Japanese JEOL systems).For MS devices, with ionization voltage 70eV, scanning range m/z=10~500, photoelectricity Multiplier tube gain 450V is measured.

Terminal primary OH ratios (%)=B ÷ A × 100 (5)

3) average grain diameter of aqueous polyurethane dispersion

The number average bead diameter of aqueous polyurethane dispersion is determined using Particle Size Analyzer Nanotrac150 (Microtrac systems) (nm)。

4) number-average molecular weight of aqueous polyurethane dispersion, molecular weight distribution

The number-average molecular weight and molecular weight distribution of aqueous polyurethane dispersion are obtained by gel permeation chromatograph (GPC). GPC devices, using 4 TSK gel Super HM-H, are used on the HLC-8220GPC devices that Tosoh Corporation are manufactured RI detectors are detected.With developing solvent dimethylformamide (DMF), flow velocity 0.5mL/ minutes, 40 DEG C of operation temperature, polyphenyl Ethene conversion is obtained.

5) tensile break strength and elongation at break

Aqueous polyurethane dispersion is injected on aluminum dish with ormal weight, after placing 24 hours at room temperature, at 60 DEG C Be heat-treated within 24 hours, made the sheet material of 500 μm of thickness.Width 6.6mm, length 60mm polyurethane are cut out by the sheet material The sample of resin film.In 23 DEG C of thermostatic chamber, use Universal Testing Machine (Zwick Corp. systems) Stretching when determining tensile break strength (MPa) and the fracture of said sample film for 5mm/ minutes with 20mm, draw speed between chuck Long rate (%).It should be noted that the sample film is additionally operable to evaluate (low temperature) flexibility and oil resistivity.

6) flexibility

With it is above-mentioned 5) shown in method tested, determine 50% when stretching while stretching (25mm) stress (MPa).Stress is got over It is low, it is evaluated as flexibility higher.

7) low-temperature pliability

The measurement site for determining device in above-mentioned tensile break strength 5) installs cryogenic thermostat mortise, implements at -20 DEG C Determine.Stress (MPa) when measure 50% is stretched (during stretching 25mm).Stress is lower, is evaluated as low-temperature pliability better.

8) oil resistivity

Measure impregnates said sample film the oil resistivity (swelling ratio) after 1 week in 23 DEG C of oleic acid.Use following numbers Formula (7) obtains oil resistivity (swelling ratio).

Oil resistivity (%)={ quality before (quality before quality-experiment after experiment)/experiment } × 100 (7)

9) film case hardness

Using aqueous polyurethane dispersion or water system soft-feel coating composition, with coating machine thickness about 2mm poly- carbonic acid On ester plate with thickness after solidification turn into about 50 μm (embodiment 1~16, comparative example 1~6), about 40 μm (embodiment 17~40, compare The mode of example 7~10) carries out application, is dried at room temperature for 24 hours, obtains film.To obtained film according to JIS K-5400 Evaluation of measuring pencil hardness.

10) cured coating film outward appearance

With surface of the visual observation with the film made with above-mentioned operation 9) equally.It can be clearly visible as orange peel shape is thin Small concavo-convex surface is judged as × (bad), can will on a small quantity see that the tiny concavo-convex surface of orange peel shape such as is judged as △ (somewhat not It is good), the tiny concavo-convex surface of orange peel shape such as will be can't see and be judged as zero (good).

11) abrasion performance

Wearing away wheel method according to JIS K5600, (abrasion are taken turns to being evaluated with the film obtained with above-mentioned operation 9) equally CS-10, counterweight 500g, 500 turns).The measurement result (mg) of Mass lost in experiment is shown.

[the polymerization example 1 of PCDL]

1,3- is put into possessing the glass system flask for being filled with the 2L of the rectifying column of regular filler and agitating device Propane diols (1,3-PDO) 760.9g (10mol), ethylene carbonate 1030g (11.7mol), at 70 DEG C after stirring and dissolving, plus Enter the butyl titanate 0.10g as catalyst.Heated in 175 DEG C of oil bath is set as, in the interior temperature 140 of flask DEG C, under 1.0~1.5kPa of vacuum, while removing a part of cut from backflow head with reflux ratio 4, react 12 hours on one side.Its Afterwards, rectifying column is replaced with into simple distillation device, heated in 180 DEG C of oil bath is set as, flask interior temperature 140~ Vacuum is reduced to 0.5kPa at 150 DEG C, so as to remove the dihydric alcohol and ethylene carbonate remained in flask.Thereafter, will The setting of oil bath is improved to 185 DEG C, while removing the dihydric alcohol of generation at 160~165 DEG C of the interior temperature of flask, on one side further Reaction 4 hours.Liquid sticky at normal temperatures is obtained by the reaction.Obtained PCDL is analyzed, by result It is shown in table 1.The PCDL is referred to as PC1.

[the polymerization example 2 of PCDL]

1,3- is put into possessing the glass system flask for being filled with the 2L of the rectifying column of regular filler and agitating device Propane diols (1,3-PDO) 760.9g (10mol), dimethyl carbonate 1053.9g (11.7mol), at 70 DEG C after stirring and dissolving, Add the butyl titanate 0.10g as catalyst.At ambient pressure, heating stirring, one are carried out at a temperature of 140~150 DEG C Side distillation removes the methanol of generation and the mixture of dimethyl carbonate, while reacting 7 hours.Thereafter, reaction temperature is made to turn into 150 DEG C~190 DEG C, make pressure turn into 10~15kPa, on one side distillation remove generation methanol and dimethyl carbonate mixture, one side Reaction 3 hours.Thereafter, 0.5kPa is slowly decompressed on one side, while being reacted 3 hours at 190 DEG C.Obtained by the reaction normal Sticky liquid under temperature.Obtained PCDL is analyzed, table 1 is shown the result in.The PCDL is claimed For PC2.

[the polymerization example 3 of PCDL]

1,3- is put into possessing the glass system flask for being filled with the 2L of the rectifying column of regular filler and agitating device Propane diols (1,3-PDO) 760.9g (10mol), dimethyl carbonate 1053.9g (11.7mol), at 70 DEG C after stirring and dissolving, Add the butyl titanate 0.10g as catalyst.

At ambient pressure, heating stirring is carried out at a temperature of 140~150 DEG C, while distillation removes the methanol and carbon of generation The mixture of dimethyl phthalate, while reacting 7 hours.Thereafter, make reaction temperature turn into 150 DEG C~190 DEG C, make pressure turn into 10~ 15kPa, while distillation removes the methanol of generation and the mixture of dimethyl carbonate, while reacting 3 hours.And then at 190 DEG C Reaction 1 hour, 1,3-PD is distilled and removed.Liquid sticky at normal temperatures is obtained by the reaction.To obtained poly- carbonic acid Esterdiol is analyzed, and shows the result in table 1.The PCDL is referred to as PC3.

[the polymerization example 4 of PCDL]

1,3- is put into possessing the glass system flask for being filled with the 2L of the rectifying column of regular filler and agitating device Propane diols (1,3-PDO) 760.9g (10mol), ethylene carbonate 1030g (11.7mol), at 70 DEG C after stirring and dissolving, plus Enter the butyl titanate 0.10g as catalyst.Heated in 175 DEG C of oil bath is set as, in the interior temperature 140 of flask DEG C, under 1.0~1.5kPa of vacuum, while removing a part of cut from backflow head with reflux ratio 4, react 12 hours on one side.Its Afterwards, rectifying column is replaced with into simple distillation device, heated in 180 DEG C of oil bath is set as, flask interior temperature 140~ Vacuum is reduced to 0.5kPa at 150 DEG C, so as to remove the dihydric alcohol and ethylene carbonate remained in flask.Thereafter, will The setting of oil bath is improved to 185 DEG C, while removing the dihydric alcohol of generation at 160~165 DEG C of the interior temperature of flask, on one side further Reaction 4 hours.Make after normal pressure, to add 1-heptanol 3.5g (0.03mol), 3 are reacted at 160~165 DEG C of the interior temperature of flask Hour.Liquid sticky at normal temperatures is obtained by the reaction.Obtained PCDL is analyzed, table is shown the result in 1.The PCDL is referred to as PC4.

[the polymerization example 5 of PCDL]

Making the amount of 1-heptanol turns into 11.6g (0.1mol), in addition, with shown in the polymerization example 4 of PCDL Method is reacted.Liquid sticky at normal temperatures is obtained by the reaction.Obtained PCDL is analyzed, will be tied Fruit is shown in table 1.The PCDL is referred to as PC5.

[the polymerization example 6 of PCDL]

Isosorbide-5-Nitrae-cyclohexanediol 10.5g (0.09mol) is added in raw material, in addition, with gathering for PCDL The method shown in example 2 is closed to be reacted.Liquid sticky at normal temperatures is obtained by the reaction.Obtained PCDL is entered Row analysis, shows the result in table 1.The PCDL is referred to as PC6.

[the polymerization example 7 of PCDL]

1,4- is put into possessing the glass system flask for being filled with the 2L of the rectifying column of regular filler and agitating device Butanediol (Isosorbide-5-Nitrae-BDO) 901.2g (10mol), dimethyl carbonate 1053.9g (11.7mol), at 70 DEG C after stirring and dissolving, Add the butyl titanate 0.10g as catalyst.At ambient pressure, heating stirring, one are carried out at a temperature of 140~150 DEG C Side distillation removes the methanol of generation and the mixture of dimethyl carbonate, while reacting 7 hours.Thereafter, reaction temperature is made to turn into 150 DEG C~190 DEG C, make pressure turn into 10~15kPa, on one side distillation remove generation methanol and dimethyl carbonate mixture, one side Reaction 3 hours.Thereafter, 0.5kPa is slowly decompressed on one side, while being reacted 3 hours at 190 DEG C.By gathering that the reaction is obtained Carbonate diol is solid at normal temperatures.Obtained PCDL is analyzed, table 1 is shown the result in.By the poly- carbon Acid esters glycol is referred to as PC7.

[the polymerization example 8 of PCDL]

2- first is put into possessing the glass system flask for being filled with the 2L of the rectifying column of regular filler and agitating device Base -1,3-PD (MPD) 901.2g (10mol), dimethyl carbonate 1053.9g (11.7mol), at 70 DEG C stirring and dissolving it Afterwards, the butyl titanate 0.10g as catalyst is added.

At ambient pressure, heating stirring is carried out at a temperature of 140~150 DEG C, while distillation removes the methanol and carbon of generation The mixture of dimethyl phthalate, while reacting 7 hours.Thereafter, make reaction temperature turn into 150 DEG C~190 DEG C, make pressure turn into 10~ 15kPa, while distillation removes the methanol of generation and the mixture of dimethyl carbonate, while reacting 3 hours.Thereafter, it is slow on one side Ground is decompressed to 0.5kPa, while being reacted 3 hours at 190 DEG C.Liquid sticky at normal temperatures is obtained by the reaction.To what is obtained PCDL is analyzed, and shows the result in table 1.The PCDL is referred to as PC8.

[the polymerization example 9 of PCDL]

1,5- is put into possessing the glass system flask for being filled with the 2L of the rectifying column of regular filler and agitating device Pentanediol (1,5-PDO) 385g (3.7mol), 1,6-HD (1,6-HDO) 385g (3.26mol), dimethyl carbonate 1053.9g (11.7mol), at 70 DEG C after stirring and dissolving, adds the butyl titanate 0.10g as catalyst.

At ambient pressure, heating stirring is carried out at a temperature of 140~150 DEG C, while distillation removes the methanol and carbon of generation The mixture of dimethyl phthalate, while reacting 7 hours.Thereafter, make reaction temperature turn into 150 DEG C~190 DEG C, make pressure turn into 10~ 15kPa, while distillation removes the ethylene glycol of generation and the mixture of ethylene carbonate, while reacting 3 hours.Thereafter, while slow 0.5kPa is slowly decompressed to, while being reacted 3 hours at 190 DEG C.Liquid sticky at normal temperatures is obtained by the reaction.To obtaining PCDL analyzed, show the result in table 1.The PCDL is referred to as PC9.

[table 1]

[embodiment 1]

Under nitrogen atmosphere, add in possessing mixer, cooling tube, nitrogen inflow pipe, the 1000ml of thermometer 4 mouthfuls of flasks Enter IPDI (IPDI) 33.3g (0.15 mole), 100g (0.05 mole) PCDL PC1, two Hydroxymethyl propionic acid (DMPA) 6.7g (0.05 mole), triethylamine (TEA) 6.1g (0.05 mole) and MEK (MEK) 30ml, Reacted 2.5 hours at 80 DEG C, obtain the pre-polymer solution of NCO ends.Then, add deionized water 342g, at 35 DEG C with Pre-polymer solution is mixed, and obtains prepolymer dispersion.Ethylenediamine (EDA) 1.5g will be included in deionized water 2.0g The solution of (0.0025 mole) is added in prepolymer dispersion, is stirred 1 hour at 30 DEG C.Then, by mixture at 80 DEG C Lower heating, removes MEK, so as to obtain the aqueous polyurethane dispersion with solid constituent 30%.By obtained aqueous polyurethane The characteristic of dispersion (PUD1) is summarised in table 2.

[embodiment 2]

PC2 is used instead of PCDL PC1, in addition, is reacted similarly to Example 1, obtains water It is dispersions of polyurethanes.The characteristic of obtained aqueous polyurethane dispersion (PUD2) is summarised in table 2.

[embodiment 3]

Under nitrogen atmosphere, add in possessing mixer, cooling tube, nitrogen inflow pipe, the 1000ml of thermometer 4 mouthfuls of flasks Enter IPDI (IPDI) 66.6g (0.3 mole), 100g (0.1 mole) PCDL PC3, dihydroxy Methylpropanoic acid (DMPA) 13.4g (0.1 mole), triethylamine (TEA) 12.2g (0.1 mole) and MEK (MEK) 30ml, Reacted 2.5 hours at 80 DEG C, obtain the pre-polymer solution of NCO ends.Then, deionized water 427g is added, it is at 35 DEG C and pre- Copolymer solution is mixed, and obtains prepolymer dispersion.By comprising ethylenediamine (EDA) 3.0g, (0.005 rubs in deionized water 2.0g You) solution be added in prepolymer dispersion, at 30 DEG C stir 1 hour.Then, mixture is heated at 80 DEG C, gone Except MEK, so as to obtain the aqueous polyurethane dispersion with solid constituent 30%.By obtained aqueous polyurethane dispersion (PUD3) characteristic is summarised in table 2.

[embodiment 4]

PC4 is used instead of PCDL PC1, in addition, is reacted similarly to Example 1, obtains water It is dispersions of polyurethanes.The characteristic of obtained aqueous polyurethane dispersion (PUD4) is summarised in table 2.

[embodiment 5]

PC5 is used instead of PCDL PC1, in addition, is reacted similarly to Example 1, obtains water It is dispersions of polyurethanes.The characteristic of obtained aqueous polyurethane dispersion (PUD5) is summarised in table 2.

[embodiment 6]

PC6 is used instead of PCDL PC1, in addition, is reacted similarly to Example 1, obtains water It is dispersions of polyurethanes.The characteristic of obtained aqueous polyurethane dispersion (PUD6) is summarised in table 2.

[embodiment 7]

PC2 is used instead of PCDL PC1, the isocyanide of hexa-methylene two is made instead of IPDI Acid esters is 25.2g (0.15 mole), in addition, is reacted similarly to Example 1, obtains aqueous polyurethane dispersion. The characteristic of obtained aqueous polyurethane dispersion (PUD7) is summarised in table 2.

[embodiment 8]

PC2 is used instead of PCDL PC1, instead of IPDI by 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate) is set to 39.4g (0.15 mole), in addition, is reacted similarly to Example 1, obtains water system Dispersions of polyurethanes.The characteristic of obtained aqueous polyurethane dispersion (PUD8) is summarised in table 2.

[comparative example 1]

PC7 is used instead of PCDL PC2, in addition, is reacted similarly to Example 2, obtains water It is dispersions of polyurethanes.The characteristic of obtained aqueous polyurethane dispersion (PUD9) is summarised in table 2.

[comparative example 2]

PC8 is used instead of PCDL PC2, in addition, is reacted similarly to Example 2, obtains water It is dispersions of polyurethanes.The characteristic of obtained aqueous polyurethane dispersion (PUD10) is summarised in table 2.

[comparative example 3]

PC9 is used instead of PCDL PC2, in addition, is reacted similarly to Example 2, obtains water It is dispersions of polyurethanes.The characteristic of obtained aqueous polyurethane dispersion (PUD11) is summarised in table 2.

[table 2]

[embodiment 9]

{ evaluation of water system soft-feel coating composition }

By 300g aqueous polyurethane dispersion PUD1, water system with levelling agent BYK-3455 (BYK chemical Co., Ltd. make) 2.06g, polyurethane particles (ArtPearl, C-800, average grain diameter=6 μm, Negami Chemical Ind Co., Ltd.'s system) 35g mix Stirring is closed, water system soft-feel coating composition is obtained.It is coated on acrylonitrile-butadiene-styrene (ABS) (ABS) resin plate it Afterwards, heat drying 2 hours at 80 DEG C, obtain the film of 30~40 μm of thickness.Its various physical property is shown in table 3.In table 3, lead to Sense of touch when touching film plate surface with hand is crossed to evaluate soft feeling.Result of determination is represented with following mark.

○：With the sense of touch as natural leather, good soft feeling

△：With the sense of touch as natural leather, better soft feeling

×：Without the sense of touch as natural leather, imperceptible softness

[embodiment 10~16, comparative example 4~6]

PUD2~11 are used instead of PUD1, water system soft-feel coating composition is obtained similarly to Example 9.Its is various Physical property is shown in table 3.

[table 3]

[the polymerization example 10 of PCDL]

1,3- is put into possessing the glass system flask for being filled with the 2L of the rectifying column of regular filler and agitating device Propane diols (1,3-PDO) 456.5g (6mol), 1,4- butanediols (1,4-BDO) 360.5g (4mol), ethylene carbonate 1030g (11.7mol), at 70 DEG C after stirring and dissolving, adds the butyl titanate 0.10g as catalyst.It is being set as 175 DEG C Oil bath in heated, under 140 DEG C of the interior temperature, 1.0~1.5kPa of vacuum in flask, while from backflow head with reflux ratio 4 A part of cut is removed, while reacting 12 hours.Thereafter, rectifying column is replaced with into simple distillation device, is set as 180 DEG C of oil Heated in bath, vacuum is reduced to 0.5kPa at 140~150 DEG C of the interior temperature of flask, flask is remained in so as to remove Interior dihydric alcohol and ethylene carbonate.Thereafter, the setting of oil bath is improved to 185 DEG C, at 160~165 DEG C of the interior temperature of flask While removing the dihydric alcohol of generation, further react 4 hours on one side.Liquid sticky at normal temperatures is obtained by the reaction.To To PCDL analyzed, show the result in table 4.The PCDL is referred to as PC10.

[the polymerization example 11 of PCDL]

1,3- is put into possessing the glass system flask for being filled with the 2L of the rectifying column of regular filler and agitating device Propane diols (1,3-PDO) 456.5g (6mol), BDO (Isosorbide-5-Nitrae-BDO) 360.5g (4mol), dimethyl carbonate 1053.9g (11.7mol), at 70 DEG C after stirring and dissolving, adds the butyl titanate 0.10g as catalyst.At ambient pressure, 140~ Heating stirring is carried out at a temperature of 150 DEG C, while distillation removes the methanol of generation and the mixture of dimethyl carbonate, it is anti-on one side Answer 7 hours.Thereafter, reaction temperature is made to turn into 150 DEG C~190 DEG C, pressure is turned into 10~15kPa, while distillation removes generation Methanol and dimethyl carbonate mixture, while reaction 3 hours.Thereafter, 0.5kPa is slowly decompressed on one side, while Reacted 3 hours at 190 DEG C.Liquid sticky at normal temperatures is obtained by the reaction.Obtained PCDL is analyzed, Show the result in table 4.The PCDL is referred to as PC11.

[the polymerization example 12 of PCDL]

1,5-PD (1,5-PDO) is set to 416.6g (4mol) instead of BDO, in addition, poly- carbon is used Method shown in the polymerization example 11 of acid esters glycol is reacted.Liquid sticky at normal temperatures is obtained by the reaction.To what is obtained PCDL is analyzed, and shows the result in table 4.The PCDL is referred to as PC12.

[the polymerization example 13 of PCDL]

1,6- hexylene glycols (1,6-HDO) are set to 472.7g (4mol) instead of BDO, in addition, poly- carbon are used Method shown in the polymerization example 11 of acid esters glycol is reacted.By the reaction, sticky liquid is obtained at normal temperatures.To what is obtained PCDL is analyzed, and shows the result in table 4.The PCDL is referred to as PC13.

[the polymerization example 14 of PCDL]

The amount of 1,3-PD (1,3-PDO) is set to 608.7g (8mol), the amount of BDO (Isosorbide-5-Nitrae-BDO) is set For 180.2g (2mol), in addition, reacted with the method shown in the polymerization example 11 of PCDL.Reacted by this To liquid sticky at normal temperatures.Obtained PCDL is analyzed, table 4 is shown the result in.By the makrolon Glycol is referred to as PC14.

[the polymerization example 15 of PCDL]

The amount of 1,3- propane diols (1,3-PDO) is set to 228.2g (3mol), the amount of 1,4- butanediols (1,4-BDO) is set For 630.8g (7mol), in addition, reacted with the method shown in the polymerization example 11 of PCDL.Reacted by this To liquid sticky at normal temperatures.Obtained PCDL is analyzed, table 1 is shown the result in.By the makrolon Glycol is referred to as PC6.

[the polymerization example 16 of PCDL]

1,3- is put into possessing the glass system flask for being filled with the 2L of the rectifying column of regular filler and agitating device Propane diols (1,3-PDO) 456.5g (6mol), BDO (Isosorbide-5-Nitrae-BDO) 360.5g (4mol), dimethyl carbonate 1053.9g (11.7mol), at 70 DEG C after stirring and dissolving, adds the butyl titanate 0.10g as catalyst.

At ambient pressure, heating stirring is carried out at a temperature of 140~150 DEG C, while distillation removes the methanol and carbon of generation The mixture of dimethyl phthalate, while reacting 7 hours.Thereafter, make reaction temperature turn into 150 DEG C~190 DEG C, make pressure turn into 10~ 15kPa, while distillation removes the methanol of generation and the mixture of dimethyl carbonate, while reacting 3 hours.And then at 190 DEG C Reaction 1 hour, 1,3-PD is distilled and removed.Liquid sticky at normal temperatures is obtained by the reaction.To obtained poly- carbonic acid Esterdiol is analyzed, and shows the result in table 4.The PCDL is referred to as PC16.

[the polymerization example 17 of PCDL]

1,3- is put into possessing the glass system flask for being filled with the 2L of the rectifying column of regular filler and agitating device Propane diols (1,3-PDO) 456.5g (6mol), BDO (Isosorbide-5-Nitrae-BDO) 360.5g (4mol), ethylene carbonate 1030g (11.7mol), at 70 DEG C after stirring and dissolving, adds the butyl titanate 0.10g as catalyst.It is being set as 175 DEG C Oil bath in heated, under 140 DEG C of the interior temperature, 1.0~1.5kPa of vacuum in flask, while from backflow head with reflux ratio 4 A part of cut is removed, while reacting 12 hours.Thereafter, rectifying column is replaced with into simple distillation device, is set as 180 DEG C of oil Heated in bath, vacuum is reduced to 0.5kPa at 140~150 DEG C of the interior temperature of flask, flask is remained in so as to remove Interior dihydric alcohol and ethylene carbonate.Thereafter, the setting of oil bath is improved to 185 DEG C, at 160~165 DEG C of the interior temperature of flask While removing the dihydric alcohol of generation, further react 4 hours on one side.Make after normal pressure, to add 1-heptanol 5.8g (0.05mol), reacts 3 hours at 160~165 DEG C of the interior temperature of flask.Liquid sticky at normal temperatures is obtained by the reaction.It is right Obtained PCDL is analyzed, and shows the result in table 4.The PCDL is referred to as PC17.

[the polymerization example 18 of PCDL]

The amount of 1-heptanol is set to 11.6g (0.1mol), in addition, with shown in the polymerization example 17 of PCDL Method is reacted.Liquid sticky at normal temperatures is obtained by the reaction.Obtained PCDL is analyzed, will be tied Fruit is shown in table 1.The PCDL is referred to as PC18.

[the polymerization example 19 of PCDL]

Isosorbide-5-Nitrae-cyclohexanediol 10.5g (0.09mol) is appended in raw material, in addition, with gathering for PCDL The method shown in example 11 is closed to be reacted.Liquid sticky at normal temperatures is obtained by the reaction.To obtained PCDL Analyzed, show the result in table 4.The PCDL is referred to as PC19.

[the polymerization example 20 of PCDL]

The amount of 1,3- propane diols (1,3-PDO) is set to 114.1g (1.5mol), the amount by 1,4- butanediols (1,4-BDO) 766.0g (8.5mol) is set to, in addition, is reacted with the method shown in the polymerization example 11 of PCDL.It is anti-by this Liquid sticky at normal temperatures should be obtained.Obtained PCDL is analyzed, table 4 is shown the result in.By the poly- carbon Acid esters glycol is referred to as PC20.

[the polymerization example 21 of PCDL]

At ambient pressure, heating stirring is carried out at a temperature of 140~150 DEG C, while distillation removes the methanol and carbon of generation The mixture of dimethyl phthalate, while reacting 7 hours.Thereafter, make reaction temperature turn into 150 DEG C~190 DEG C, make pressure turn into 10~ 15kPa, while distillation removes the ethylene glycol of generation and the mixture of ethylene carbonate, while reacting 3 hours.Thereafter, while slow 0.5kPa is slowly decompressed to, while being reacted 3 hours at 190 DEG C.Liquid sticky at normal temperatures is obtained by the reaction.To obtaining PCDL analyzed, show the result in table 4.The PCDL is referred to as PC21.

[table 4]

[embodiment 17]

Under nitrogen atmosphere, add in possessing mixer, cooling tube, nitrogen inflow pipe, the 1000ml of thermometer 4 mouthfuls of flasks Enter IPDI (IPDI) 33.3g (0.15 mole), 100g (0.05 mole) PCDL PC1, two Hydroxymethyl propionic acid (DMPA) 6.7g (0.05 mole), triethylamine (TEA) 6.1g (0.05 mole) and MEK (MEK) 30ml, Reacted 2.5 hours at 80 DEG C, obtain the pre-polymer solution of NCO ends.Then, add deionized water 342g, at 35 DEG C with Pre-polymer solution is mixed, and obtains prepolymer dispersion.Ethylenediamine (EDA) 1.5g will be included in deionized water 2.0g The solution of (0.0025 mole) is added in prepolymer dispersion, is stirred 1 hour at 30 DEG C.Then, heat the mixture to 80 DEG C and remove MEK, so as to obtain the aqueous polyurethane dispersion with solid constituent 30%.By obtained aqueous polyurethane point The characteristic of granular media (PUD12) is summarised in table 5.

[embodiment 18~22]

PC11, PC12, PC13, PC14, PC15 are used instead of PCDL PC10, in addition, with embodiment 17 are similarly reacted, and obtain aqueous polyurethane dispersion.By obtained aqueous polyurethane dispersion (PUD13, PUD14, PUD15, PUD16, PUD17) characteristic be summarised in table 5.

[embodiment 23]

Under nitrogen atmosphere, add in possessing mixer, cooling tube, nitrogen inflow pipe, the 1000ml of thermometer 4 mouthfuls of flasks Enter IPDI (IPDI) 66.6g (0.3 mole), 100g (0.1 mole) PCDL PC16, dihydroxy Methylpropanoic acid (DMPA) 13.4g (0.1 mole), triethylamine (TEA) 12.2g (0.1 mole) and MEK (MEK) 30ml, Reacted 2.5 hours at 80 DEG C, obtain the pre-polymer solution of NCO ends.Then, deionized water 427g is added, it is at 35 DEG C and pre- Copolymer solution is mixed, and obtains prepolymer dispersion.By comprising ethylenediamine (EDA) 3.0g, (0.005 rubs in deionized water 2.0g You) solution be added in prepolymer dispersion, at 30 DEG C stir 1 hour.Then, 80 DEG C are heated the mixture to and is removed MEK, so as to obtain the aqueous polyurethane dispersion with solid constituent 30%.By obtained aqueous polyurethane dispersion (PUD18) characteristic is summarised in table 5.

[embodiment 24~26]

PC17, PC18, PC19 are used instead of PCDL PC10, in addition, is entered similarly to Example 17 Row reaction, obtains aqueous polyurethane dispersion.By obtained aqueous polyurethane dispersion (PUD19, PUD20, PUD21) characteristic It is summarised in table 5.

[embodiment 27]

PC11 is used instead of PCDL PC10, makes hexa-methylene two different instead of IPDI Cyanate turns into 25.2g (0.15 mole), in addition, is reacted similarly to Example 17, obtains aqueous polyurethane point Granular media.The characteristic of obtained aqueous polyurethane dispersion (PUD22) is summarised in table 5.

[embodiment 28]

PC11 is used instead of PCDL PC10, instead of IPDI by 4,4 '-methylene Double (cyclohexyl isocyanates) are set to 39.4g (0.15 mole), in addition, are reacted, obtained similarly to Example 17 Aqueous polyurethane dispersion.The characteristic of obtained aqueous polyurethane dispersion (PUD23) is summarised in table 5.

[comparative example 7,8]

PC20, PC21 are used instead of PCDL PC11, in addition, is reacted similarly to Example 18 And obtain aqueous polyurethane dispersion.The characteristic of obtained aqueous polyurethane dispersion (PUD24, PUD25) is summarised in table 5.

[table 5]

[embodiment 29]

(evaluation of water borne soft-feel coating composition)

By PUD12 aqueous polyurethane dispersion 300g, aqueous use levelling agent BYK-3455 (BYK chemical Co., Ltd. make) 2.06g, polyurethane particles (ArtPearl, C-800, average grain diameter=6 μm, Negami Chemical Ind Co., Ltd.'s system) 35g mix Stirring is closed, water borne soft-feel coating composition is obtained.It is applied on acrylonitrile-butadiene-styrene (ABS) (ABS) resin plate it Afterwards, heat drying 2 hours at 80 DEG C, obtain the film of 30~40 μm of thickness.Its various physical property is shown in table 6.In table 6, lead to Sense of touch when touching film plate surface with hand is crossed to evaluate soft feeling.Result of determination is represented with following mark.

○：With the sense of touch as natural leather, good soft feeling

△：With the sense of touch as natural leather, better soft feeling

×：Without the sense of touch as natural leather, imperceptible softness

[embodiment 30~40, comparative example 9~10]

PUD13~25 are used instead of PUD12, water borne soft-feel coating composition is obtained similarly to Example 29.By its Various physical property are shown in table 6.

[table 6]

Industrial applicability

The aqueous polyurethane dispersion of the present invention can be preferably used for an electrical article, OA products, automotive interior part, skin Surface treatment of leather etc..

Claims

1. a kind of aqueous polyurethane dispersion, it includes water-dispersible polyurethane and water, and the water-dispersible polyurethane is (a) 1 Organic polyisocyanate compound, (b) PCDL and (c) containing the NCO of more than 2 in molecule contain There are carboxyl and/or the polyalcohol of sulfo group or the reaction product of its salt,

(b) PCDL be with the repeat unit and the PCDL of terminal hydroxyl shown in following formula (1), The construction unit shown in following formula (2) comprising 20 moles of more than % in construction unit shown in formula (1),

In formula, R₁The aliphatic hydrocarbon or clicyclic hydrocarbon of the divalence of carbon number 2~20 are represented,

2. aqueous polyurethane dispersion according to claim 1, wherein, (b) PCDL is in the formula (1) The construction unit shown in the formula (2) for being more than 90 moles of % is included in shown construction unit.

3. aqueous polyurethane dispersion according to claim 2, wherein, the terminal primary hydroxyl of (b) PCDL Base (OH) ratio is more than 95% and less than 99.5%, and the number-average molecular weight of (b) PCDL is 300~5000.

4. the aqueous polyurethane dispersion according to Claims 2 or 3, wherein, (a) organic polyisocyanate compound For aliphatic organic diisocyanate compound and/or alicyclic organic diisocyanate compound.

5. a kind of water system soft-feel coating composition, its aqueous polyurethane for containing any one of claim 2~4 disperses Body.

6. aqueous polyurethane dispersion according to claim 1, wherein, (b) PCDL is in the formula (1) The construction unit shown in the formula (2) comprising 20 moles of more than % and 90 mole of below % in shown construction unit.

7. aqueous polyurethane dispersion according to claim 6, wherein, the terminal primary hydroxyl of (b) PCDL Base (OH) ratio is more than 95% and less than 99.5%, and the number-average molecular weight of (b) PCDL is 300~5000.

8. the aqueous polyurethane dispersion according to claim 6 or 7, wherein, (a) organic polyisocyanate compound For aliphatic organic diisocyanate compound and/or alicyclic organic diisocyanate compound.

9. a kind of water system soft-feel coating composition, its aqueous polyurethane for containing any one of claim 6~8 disperses Body.