CN104004160B - Soft feeling coating high thixotroping aqueous polyurethane dispersion and its preparation method - Google Patents
Soft feeling coating high thixotroping aqueous polyurethane dispersion and its preparation method Download PDFInfo
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- CN104004160B CN104004160B CN201410268071.XA CN201410268071A CN104004160B CN 104004160 B CN104004160 B CN 104004160B CN 201410268071 A CN201410268071 A CN 201410268071A CN 104004160 B CN104004160 B CN 104004160B
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/4833—Polyethers containing oxyethylene units
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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Abstract
The present invention discloses soft feeling coating high thixotroping aqueous polyurethane dispersion and its preparation method, and wherein preparation method comprises the steps: that S1. adds polyether Glycols, vulcabond, catalyzer; S2. add small molecular alcohol and obtain base polyurethane prepolymer for use as A; S3. polymer polyatomic alcohol, vulcabond, catalyzer is added; S4. add the unit molecule dibasic alcohol of carboxyl, obtain base polyurethane prepolymer for use as B; S5. mix; S6. add emulsifying agent or the aqueous solution of protective colloid formation, dispersion, then add polyamine. The dispersion that the soft feeling coating of the present invention is prepared by the preparation method of high thixotroping aqueous polyurethane dispersion not only has strong Flexible, and tack, the intensity after film all obtains comprehensive improvement. Meanwhile, the dispersion obtained by the preparation method of the present invention has high thixotropic, has greatly saved the cost being added thickening material, anti-sedimentation agent and thixotropic agent for improving storage stability.
Description
Technical field
The present invention relates to the field of chemical synthesis, particularly relate to a kind of soft feeling coating high thixotroping aqueous polyurethane dispersion and its preparation method.
Background technology
Soft feeling coating, what namely resin-coating was formed on base material has a kind of coating of submissive feel. Above-mentioned soft feeling is sometimes also known as elastic handfeel or fuzzy hand, and coating and the elastic coating with soft feeling have essential distinction, and elastic coating refers to that film has high elongation at break, and touch feeling is not done requirement.
At present, soft feeling coating is mainly used in three aspects: one, in most cases, it is possible to is coated on BOPP or BOPET as precoating flexible packaging film by roll coating model and uses; Two, it is applied in various electronics or electric equipment products, after machine-shaping, all needs the coating in the touch of surface spraying protection and decoration with elastic handfeel such as shells such as digital camera, notebook computer, mobile phones; Three, it is widely used on clothing leather, sofa leather and automobile cushion leather as hide finishes.
At present, preparation method about soft feeling coating adds elasticity powder or fine hair powder (refine such as big day 5070D) in resin (vibrin, Synolac, acrylic resin and urethane etc.), it may also be useful to various dispersion agent, anti-sedimentation agent etc. make powder be dispersed in the coating formed in resin.
Such as, the patent No. is 201110183769.8, and name is called the patent of a kind of spraying elastic polyurethane handfeel paint coating and purposes, discloses the preparation method of a kind of elastic handfeel paint being used in electronic product casing. This kind of method mainly fills the sub-light powder of elasticity in two kinds of vibrin containing hydroxyl, adds appropriate isocyanate curing agent and make film continuous before spraying, and intensity increases.But the shortcoming in technique scheme is to employ dimethylbenzene and N-BUTYL ACETATE. Although these two kinds is low poison reagent in organic solvent, but it is produce unhappy smell in construction process unavoidably, cause the health hazards of human body. Secondly, because needing to add powder, although the vibrin containing hydroxyl can be good at powder lot dispersing, but long storage time, and its stability there will be problem. In addition, elasticity powder commercially available at present or fine hair powder are expensive, and need to reach Flexible, often need the powder scale of construction added to be exceeded more than the 20% of coating, and for coating business and human consumer, cost is too expensive.
Therefore, for the problems referred to above, it is necessary to provide a kind of improvement scheme further.
Summary of the invention
In view of this, the present invention provides a kind of soft feeling coating high thixotroping aqueous polyurethane dispersion and its preparation method, which overcomes in the existing method preparing soft feeling coating the drawback brought by adding elasticity powder, fine hair powder etc.
The preparation method of the present invention is based on following technical conceive: the urethane resin that the structure of the polyaminoester microball of soft feeling needs need to possess certain flexibility, but also needs to have certain hardness and toughness. Because make urethane resin intensity not high if in order to pursue soft feeling, not only easily cave in when coating film forming, and the film bulk strength formed is inadequate, it is easy to damaged. And if by add linking agent make urethane resin have high compactness, so Flexible will disappear. Above-mentioned technical requirements has good soft feeling to being formed and has again that the urethane of certain intensity is micro-constitutes one pair of contradiction, therefore, need to consider above-mentioned technical requirements, balance relation therebetween.
Thus, it is a kind of interior soft outer close that the soft feeling coating of the present invention is intended to synthesis by the preparation method of high thixotroping aqueous polyurethane dispersion, and has the polyaminoester microball of certain size. This polyaminoester microball internal structure is base polyurethane prepolymer for use as A, and the molecular weight of this base polyurethane prepolymer for use as A is lower, and it does not remain isocyanato, and hydrophobicity flexibility is good. Thus the base polyurethane prepolymer for use as A of inside makes polyaminoester microball have certain flexibility. The layer structure of polyaminoester microball is base polyurethane prepolymer for use as B, and this base polyurethane prepolymer for use as B molecular weight is higher, containing a certain amount of isocyanato on it, and finer and close, good hydrophilic property. Thus outer field base polyurethane prepolymer for use as B makes polyaminoester microball have certain stability.
First the soft feeling coating of the present invention prepares base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B by the preparation method of high thixotroping aqueous polyurethane dispersion, then the two is mixed so that the amount of outer field base polyurethane prepolymer for use as B can encase the base polyurethane prepolymer for use as A of internal layer completely. Specifically, after base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B carries out mixing, neutralizes, a certain size polyaminoester microball after water-dispersion, is formed. Wherein, owing to base polyurethane prepolymer for use as A has hydrophobicity, tend to the center at bead, and base polyurethane prepolymer for use as B has wetting ability, tend to be wrapped in around bead, material is thus formed the polyurethane aqueous dispersion body microballoon of interior soft outer close structure.
Under foregoing invention design is instructed, for realizing the object of the present invention, a kind of soft feeling coating of the present invention preparation method of high thixotroping aqueous polyurethane dispersion, its spy comprises the steps, in following steps, part number of material is in mass parts:
S1. in the first reactor, 70��90 parts of polyether Glycols are added, dehydration;Cooling, then add the vulcabond of 10��30 parts and the catalyzer of 0.1��1 part;
S2. in the first reactor, add the small molecular alcohol of excessive single functionality, continue reaction; Heating up, slough unnecessary small molecular alcohol, cooling, obtains base polyurethane prepolymer for use as A;
S3. in the 2nd reactor, the polymer polyatomic alcohol of 30��80 parts is added, dehydration; Cooling, adds the vulcabond of 20��70 parts and the catalyzer of 0.1��1 part;
S4. in the 2nd reactor, add the unit molecule dibasic alcohol containing carboxyl of 1��6 part, continue reaction; Cooling, adds neutralizing agent, obtains base polyurethane prepolymer for use as B;
S5. base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B is mixed with the mass ratio of 1:3��2:1;
S6. in the mixed system of base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B formation, add the emulsifying agent of 5��30 parts or the aqueous solution of protective colloid formation, dispersion, then add polyamine in mixed system, obtain target product.
As a further improvement on the present invention, in S1, described polyether Glycols comprises the one in polyoxyethylene glycol, polypropylene glycol, polytetrahydrofuran diol or two or more.
As a further improvement on the present invention, in S1, the scope of the molecular weight of described polyether Glycols is 2000��8000.
As a further improvement on the present invention, in S1 and S3, described vulcabond is a kind of in isophorone diisocyanate, hexamethylene diisocyanate or both combinations.
As a further improvement on the present invention, in S1 and S3, described catalyzer is tertiary amine catalyst, organic tin catalyzer or organo-bismuth class catalyzer.
As a further improvement on the present invention, described S1 specifically comprises: add 70��90 parts of polyether Glycols in the first reactor, vacuum hydro-extraction 2h under at least 100 DEG C of conditions; It is cooled to 50��90 DEG C, then adds the vulcabond of 10��30 parts and the catalyzer of 0.1��1 part, reaction 2��5h.
As a further improvement on the present invention, in S2, described small molecular alcohol is selected from methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, ethylene glycol mono-ether, ethylene glycol ester, propylene glycol monoether, propylene glycol monoester, glycerol diether.
As a further improvement on the present invention, described S2 specifically comprises: the small molecular alcohol adding excessive single functionality in the first reactor, continues to react at least 1h; Being warming up at least 80 DEG C, vacuum sloughs unnecessary small molecular alcohol, is cooled to 60 DEG C, obtains base polyurethane prepolymer for use as A.
As a further improvement on the present invention, in S3, polymer polyatomic alcohol is a kind of in polyether polyol and polyester polyol or both combinations.
As a further improvement on the present invention, described S3 specifically comprises: the polymer polyatomic alcohol adding 30��80 parts in the 2nd reactor, vacuum hydro-extraction 2h under at least 100 DEG C of conditions; It is cooled to 50��90 DEG C, then adds the vulcabond of 20��70 parts and the catalyzer of 0.1��1 part, reaction 2h.
As a further improvement on the present invention, in S4, the described unit molecule dibasic alcohol containing carboxyl is two hydroxymethyl propionic acid and the one in two hydroxymethylbutyrate or the two combination.
As a further improvement on the present invention, described S4 specifically comprises: the unit molecule dibasic alcohol containing carboxyl adding 1��6 part in the 2nd reactor, continues reaction 1��3h; Being cooled to less than 60 DEG C, add tertiary amine neutralization, obtain base polyurethane prepolymer for use as B, described tertiary amine is a kind of in triethylamine and trolamine or both combinations.
As a further improvement on the present invention, when base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B is mixed by described S5, also comprise and add acetone in the mixed system of base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B formation.
As a further improvement on the present invention, in S6, described emulsifying agent and protective colloid are anionic emulsifier, cationic emulsifier, zwitter-ion emulsifying agent, nonionic emulsifying agent.
As a further improvement on the present invention, in S6, polyamine is the one in diethylenetriamine and triethylene tetramine or the two combination.
The present invention also provides a kind of high thixotroping aqueous polyurethane dispersion of soft feeling coating, and it obtains according to preparation method described above.
Compared with prior art, the invention has the beneficial effects as follows: the dispersion that the soft feeling coating of the present invention is prepared by the preparation method of high thixotroping aqueous polyurethane dispersion not only has strong Flexible, and tack, the intensity after film all obtains comprehensive improvement.
Meanwhile, the dispersion obtained by the preparation method of the present invention has high thixotropic, has greatly saved the cost being added thickening material, anti-sedimentation agent and thixotropic agent for improving storage stability.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, it is briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, the accompanying drawing that the following describes is only some embodiments recorded in the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, it is also possible to obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is the method flow schematic diagram of preparation method one embodiment of the high thixotroping aqueous polyurethane dispersion of soft feeling coating of the present invention.
Embodiment
As shown in Figure 1, the present invention discloses the preparation method of a kind of soft feeling coating with high thixotroping aqueous polyurethane dispersion, and it comprises the steps, in following steps, part number of material is in mass parts:
S1. in the first reactor, 70��90 parts of polyether Glycols are added, dehydration; Cooling, then add the vulcabond of 10��30 parts and the catalyzer of 0.1��1 part;
S2. in the first reactor, add the small molecular alcohol of excessive single functionality, continue reaction; Heating up, slough unnecessary small molecular alcohol, cooling, obtains base polyurethane prepolymer for use as A;
S3. in the 2nd reactor, the polymer polyatomic alcohol of 30��80 parts is added, dehydration; Cooling, adds the vulcabond of 20��70 parts and the catalyzer of 0.1��1 part;
S4. in the 2nd reactor, add the unit molecule dibasic alcohol containing carboxyl of 1��6 part, continue reaction; Cooling, adds neutralizing agent, obtains base polyurethane prepolymer for use as B;
S5. base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B is mixed with the mass ratio of 1:3��2:1;
S6. in the mixed system of base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B formation, add the emulsifying agent of 5��30 parts or the aqueous solution of protective colloid formation, dispersion, then add polyamine in mixed system, obtain target product.
To achieve the object of the present invention, described S1 specifically comprises: add 70��90 parts of polyether Glycols in the first reactor, vacuum hydro-extraction 2h under at least 100 DEG C of conditions; It is cooled to 50��90 DEG C, then adds the vulcabond of 10��30 parts and the catalyzer of 0.1��1 part, reaction 2��5h.
In present embodiment, the scope of the molecular weight of described polyether Glycols is 2000��8000, it is preferable to 4000��6000.Described polyether Glycols can comprise the one in polyoxyethylene glycol, polypropylene glycol, polytetrahydrofuran diol or two or more.
Described vacuum hydro-extraction preferably carries out under 120 DEG C of conditions, can select the reactor with temp regulating function and dehydrating function accordingly.
Cooling is preferably down to 80 DEG C, then adds the vulcabond of 10��30 parts and the catalyzer of 0.1��1 part, reaction 2��5h.
Described vulcabond can be a kind of in isophorone diisocyanate, hexamethylene diisocyanate or both combinations.
Described catalyzer can be tertiary amine catalyst, organic tin catalyzer or organo-bismuth class catalyzer. Preferably, catalyzer is the positive fourth tin of two lauric acid two.
To achieve the object of the present invention, described S2 specifically comprises: the small molecular alcohol adding excessive single functionality in the first reactor, continues to react at least 1h; Being warming up at least 80 DEG C, vacuum sloughs unnecessary small molecular alcohol, is cooled to 60 DEG C, obtains base polyurethane prepolymer for use as A.
In present embodiment, the small molecular alcohol of single functionality is the alcohol class only containing a hydroxyl, and the group not reacted containing other and NCO. Specifically, the small molecular alcohol of single functionality can be selected from methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, ethylene glycol mono-ether, ethylene glycol ester, propylene glycol monoether, propylene glycol monoester, glycerol diether. The small molecular alcohol of single functionality is preferably boiling point lower than the alcohol class of 80 DEG C, more preferably, and the ethanol less for toxicity and Virahol. Wherein, it may also be useful to the small molecular alcohol of excessive single functionality refers to the content of the isocyano remained after its consumption is greater than described vulcabond and polyether Glycols reaction, and described polyether Glycols and vulcabond total amount are by 100 parts. So, it is to enable isocyano fully react, avoids residual isocyano. Afterwards, unnecessary small molecular alcohol carries out volatilization by the method heated up again and removes.
To achieve the object of the present invention, described S3 specifically comprises: the polymer polyatomic alcohol adding 30��80 parts in the 2nd reactor, vacuum hydro-extraction 2h under at least 100 DEG C of conditions; It is cooled to 50��90 DEG C, then adds the vulcabond of 20��70 parts and the catalyzer of 0.1��1 part, reaction 2h.
In present embodiment, polymer polyatomic alcohol can be a kind of in polyether polyol and polyester polyol or both combinations. Wherein, the functionality of polyether polyol is preferably 2��3, and polyether polyol can be polyoxyethylene glycol, polypropylene glycol, polytetrahydrofuran diol. The functionality of polyester polyol is preferably 2��3, and polyester polyol can be aliphatic polyester, polycaprolactone, polycarbonate etc. Described polymer polyatomic alcohol and vulcabond total amount are by 100 parts.
In addition, described polymer polyatomic alcohol should at least comprise a kind of hydroxy silicon oil, and after its role is to make the high thixotroping aqueous polyurethane dispersion film of the present invention, surface has smooth performance, and the consumption of this hydroxy silicon oil is 1-6 part.
Described vulcabond can be a kind of in isophorone diisocyanate, hexamethylene diisocyanate or both combinations.
Described catalyzer can be tertiary amine catalyst, organic tin catalyzer or organo-bismuth class catalyzer. Preferably, catalyzer is the positive fourth tin of two lauric acid two.
To achieve the object of the present invention, described S4 specifically comprises: the unit molecule dibasic alcohol containing carboxyl adding 1��6 part in the 2nd reactor, continues reaction 1��3h;It is cooled to less than 60 DEG C, adds tertiary amine neutralization, obtain base polyurethane prepolymer for use as B.
In present embodiment, the described unit molecule dibasic alcohol containing carboxyl can be two hydroxymethyl propionic acid and the one in two hydroxymethylbutyrate or the two combination. Described tertiary amine can be a kind of in triethylamine and trolamine or both combinations, and the consumption of tertiary amine is identical with the consumption of the described unit molecule dibasic alcohol containing carboxyl.
When base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B is mixed by described S5, also comprise and add acetone in the mixed system of base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B formation, the consumption of the acetone added is base polyurethane prepolymer for use as A and the 0-50% of base polyurethane prepolymer for use as B total amount, it is preferable to 30%.
Wherein, adding acetone is add when viscosity is bigger, and the total amount of base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B is by 100 parts.
In order to reach the object of the present invention; described S6 specifically comprises: at 30 DEG C; the emulsifying agent of 5��30 parts or the aqueous solution of protective colloid formation is added in the mixed system that base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B is formed; high-speed stirring dispersion 30min, adds appropriate polyamine in system afterwards again.
Described emulsifying agent and protective colloid can be anionic emulsifier, cationic emulsifier, zwitter-ion emulsifying agent, nonionic emulsifying agent etc. Preferably, emulsifying agent or protective colloid are nonionic emulsifying agent OP-10. Specifically, protective colloid can be polyvinyl alcohol, Walocel MT 20.000PV, Natvosol etc., it is preferable to polyvinyl alcohol.
In the aqueous solution that emulsifying agent or protective colloid are formed, amount when water consumption is that the solid content of system is preset as 20%-50%, it is preferable that solid content is 30%. System refers to the water dispersion that base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B is formed after the aqueous dispersion containing emulsifying agent or protective colloid herein.
Polyamine is the one in diethylenetriamine and triethylene tetramine or the two combination, and the consumption of polyamine is with till having reacted the isocyano in base polyurethane prepolymer for use as B. The effect of polyamine is to increase the thixotropy of dispersion.
The present invention also provides a kind of high thixotroping aqueous polyurethane dispersion of soft feeling coating, and it obtains according to preparation method described above.
Below in conjunction with specific embodiment, the soft feeling coating of the present invention preparation method of high thixotroping aqueous polyurethane dispersion is described in detail.
Embodiment 1
The polypropylene glycol 70 parts that molecular weight is 4000 is added, 100 DEG C of vacuum hydro-extraction 2h in the first reactor; It is cooled to 80 DEG C, then adds the isophorone diisocyanate of 30 parts and the positive fourth tin of two lauric acid two of 0.1 part. In the first reactor, add 15 parts of Virahols, continue reaction 1h; It is warming up to 80 DEG C, sloughs unnecessary Virahol, be cooled to 60 DEG C, obtain base polyurethane prepolymer for use as A.
The polytetrahydrofuran of 30 parts is added and the molecular weight of 6 parts is the hydroxy silicon oil of 2000,100 DEG C of vacuum hydro-extraction 2h in the 2nd reactor; It is cooled to 50 DEG C, adds the isophorone diisocyanate of 64 parts and the positive fourth tin of two lauric acid two of 1 part. In the 2nd reactor, add two hydroxymethyl propionic acids of 6 parts, continue reaction 1h; It is cooled to 60 DEG C, adds 4.53 parts of triethylamines, obtain base polyurethane prepolymer for use as B.
25 parts of base polyurethane prepolymer for use as A and 75 part of base polyurethane prepolymer for use as B are mixed with the mass ratio of 1:3. In the mixed system that base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B is formed, add the aqueous solution that molecular weight is the water formation of the polyvinyl alcohol 3 parts of 1788, OP-10 and 271.36 part of 2 parts, dispersed with stirring 30min, adding the diethylenetriamine of 11.3 parts again in mixed system, presetting solid content in the present embodiment is 30%.
In the present embodiment, in the first reactor, the mol ratio of isocyano and hydroxyl is 7.71; In 2nd reactor, the ratio of the summation of isocyano and hydroxyl is 4.59.
Embodiment 2
The polypropylene glycol 80 parts that molecular weight is 4000 is added, 100 DEG C of vacuum hydro-extraction 2h in the first reactor; It is cooled to 80 DEG C, then adds the isophorone diisocyanate of 20 parts and the positive fourth tin of two lauric acid two of 0.5 part. In the first reactor, add 9 parts of Virahols, continue reaction 1h; It is warming up to 80 DEG C, sloughs unnecessary Virahol, be cooled to 60 DEG C, obtain base polyurethane prepolymer for use as A.
The polytetrahydrofuran of 55 parts is added and the molecular weight of 1 part is the hydroxy silicon oil of 2000,100 DEG C of vacuum hydro-extraction 2h in the 2nd reactor; It is cooled to 50 DEG C, adds the isophorone diisocyanate of 44 parts and the positive fourth tin of two lauric acid two of 0.5 part. In the 2nd reactor, add two hydroxymethyl propionic acids of 3.5 parts, continue reaction 1h; It is cooled to 60 DEG C, adds 2.68 parts of triethylamines, obtain base polyurethane prepolymer for use as B.
33.3 parts of base polyurethane prepolymer for use as A and 66.7 part of base polyurethane prepolymer for use as B are mixed with the mass ratio of 1:2. In the mixed system that base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B is formed, add the aqueous solution that formed of water that molecular weight is the polyvinyl alcohol 10 parts of 1788, the tween 80 of 10 parts and 295.56 parts, dispersed with stirring 30min, adding the diethylenetriamine of 6.67 parts again in mixed system, presetting solid content in the present embodiment is 30%.
In the present embodiment, in the first reactor, the mol ratio of isocyano and hydroxyl is 4.5; In 2nd reactor, the ratio of the summation of isocyano and hydroxyl is 3.66.
Embodiment 3
The polypropylene glycol 90 parts that molecular weight is 4000 is added, 100 DEG C of vacuum hydro-extraction 2h in the first reactor; It is cooled to 80 DEG C, then adds the isophorone diisocyanate of 10 parts and the positive fourth tin of two lauric acid two of 1 part. In the first reactor, add 2.5 parts of Virahols, continue reaction 1h; It is warming up to 80 DEG C, sloughs unnecessary Virahol, be cooled to 60 DEG C, obtain base polyurethane prepolymer for use as A.
The polytetrahydrofuran of 80 parts is added and the molecular weight of 3.5 parts is the hydroxy silicon oil of 2000,100 DEG C of vacuum hydro-extraction 2h in the 2nd reactor; It is cooled to 50 DEG C, adds the isophorone diisocyanate of 16.5 parts and the positive fourth tin of two lauric acid two of 0.1 part. In the 2nd reactor, add two hydroxymethyl propionic acids of 1 part, continue reaction 1h; It is cooled to 60 DEG C, adds 0.76 part of triethylamine, obtain base polyurethane prepolymer for use as B.
66.7 parts of base polyurethane prepolymer for use as A and 33.3 part of base polyurethane prepolymer for use as B are mixed with the mass ratio of 2:1. In the mixed system that base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B is formed, add the aqueous solution that formed of water that molecular weight is the polyvinyl alcohol 15 parts of 1788, the tween 80 of 15 parts and 304.64 parts, dispersed with stirring 30min, adding the diethylenetriamine of 0.56 part again in mixed system, presetting solid content in the present embodiment is 30%.
In the present embodiment, in the first reactor, the mol ratio of isocyano and hydroxyl is 2; In 2nd reactor, the ratio of the summation of isocyano and hydroxyl is 1.51.
Embodiment 4
The polypropylene glycol 70 parts that molecular weight is 4000 is added, 100 DEG C of vacuum hydro-extraction 2h in the first reactor; It is cooled to 80 DEG C, then adds the isophorone diisocyanate of 30 parts and the positive fourth tin of two lauric acid two of 0.1 part. In the first reactor, add 15 parts of Virahols, continue reaction 1h;It is warming up to 80 DEG C, sloughs unnecessary Virahol, be cooled to 60 DEG C, obtain base polyurethane prepolymer for use as A.
The polytetrahydrofuran of 55 parts is added and the molecular weight of 1 part is the hydroxy silicon oil of 2000,100 DEG C of vacuum hydro-extraction 2h in the 2nd reactor; It is cooled to 50 DEG C, adds the isophorone diisocyanate of 44 parts and the positive fourth tin of two lauric acid two of 0.5 part. In the 2nd reactor, add two hydroxymethyl propionic acids of 3.5 parts, continue reaction 1h; It is cooled to 60 DEG C, adds 2.68 parts of triethylamines, obtain base polyurethane prepolymer for use as B.
50 parts of base polyurethane prepolymer for use as A and 50 part of base polyurethane prepolymer for use as B are mixed with the mass ratio of 1:1. In the mixed system that base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B is formed, add the aqueous solution that formed of water that molecular weight is the polyvinyl alcohol 10 parts of 1788, the tween 80 of 10 parts and 291.67 parts, dispersed with stirring 30min, adding the diethylenetriamine of 5 parts again in mixed system, presetting solid content in the present embodiment is 30%.
In the present embodiment, in the first reactor, the mol ratio of isocyano and hydroxyl is 7.71; In 2nd reactor, the ratio of the summation of isocyano and hydroxyl is 3.66.
Embodiment 5
The polypropylene glycol 70 parts that molecular weight is 4000 is added, 100 DEG C of vacuum hydro-extraction 2h in the first reactor; It is cooled to 80 DEG C, then adds the isophorone diisocyanate of 30 parts and the positive fourth tin of two lauric acid two of 0.1 part. In the first reactor, add 15 parts of Virahols, continue reaction 1h; It is warming up to 80 DEG C, sloughs unnecessary Virahol, be cooled to 60 DEG C, obtain base polyurethane prepolymer for use as A.
The polytetrahydrofuran of 80 parts is added and the molecular weight of 3.5 parts is the hydroxy silicon oil of 2000,100 DEG C of vacuum hydro-extraction 2h in the 2nd reactor; It is cooled to 50 DEG C, adds the isophorone diisocyanate of 16.5 parts and the positive fourth tin of two lauric acid two of 0.1 part. In the 2nd reactor, add two hydroxymethyl propionic acids of 1 part, continue reaction 1h; It is cooled to 60 DEG C, adds 0.76 part of triethylamine, obtain base polyurethane prepolymer for use as B.
50 parts of base polyurethane prepolymer for use as A and 50 part of base polyurethane prepolymer for use as B are mixed with the mass ratio of 1:1. In the mixed system that base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B is formed, add the aqueous solution that molecular weight is the water formation of the polyvinyl alcohol 8 parts of 1788, OP-10 and 272.65 part of 8 parts, dispersed with stirring 30min, adding the diethylenetriamine of 0.85 part again in mixed system, presetting solid content in the present embodiment is 30%.
In the present embodiment, in the first reactor, the mol ratio of isocyano and hydroxyl is 7.71; In 2nd reactor, the ratio of the summation of isocyano and hydroxyl is 1.51.
Embodiment 6
The polypropylene glycol 80 parts that molecular weight is 4000 is added, 100 DEG C of vacuum hydro-extraction 2h in the first reactor; It is cooled to 80 DEG C, then adds the isophorone diisocyanate of 20 parts and the positive fourth tin of two lauric acid two of 0.5 part. In the first reactor, add 9 parts of Virahols, continue reaction 1h; It is warming up to 80 DEG C, sloughs unnecessary Virahol, be cooled to 60 DEG C, obtain base polyurethane prepolymer for use as A.
The polytetrahydrofuran of 30 parts is added and the molecular weight of 6 parts is the hydroxy silicon oil of 2000,100 DEG C of vacuum hydro-extraction 2h in the 2nd reactor; It is cooled to 50 DEG C, adds the isophorone diisocyanate of 64 parts and the positive fourth tin of two lauric acid two of 1 part. In the 2nd reactor, add two hydroxymethyl propionic acids of 6 parts, continue reaction 1h; It is cooled to 60 DEG C, adds 4.53 parts of triethylamines, obtain base polyurethane prepolymer for use as B.
50 parts of base polyurethane prepolymer for use as A and 50 part of base polyurethane prepolymer for use as B are mixed with the mass ratio of 1:1. In the mixed system that base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B is formed, add the aqueous solution that formed of water that molecular weight is the polyvinyl alcohol 8 parts of 1788, the tween 80 of 8 parts and 272.42 parts, dispersed with stirring 30min, adding the diethylenetriamine of 0.75 part again in mixed system, presetting solid content in the present embodiment is 30%.
In the present embodiment, in the first reactor, the mol ratio of isocyano and hydroxyl is 4.5; In 2nd reactor, the ratio of the summation of isocyano and hydroxyl is 4.59.
Embodiment 7
The polypropylene glycol 80 parts that molecular weight is 4000 is added, 100 DEG C of vacuum hydro-extraction 2h in the first reactor; It is cooled to 80 DEG C, then adds the isophorone diisocyanate of 20 parts and the positive fourth tin of two lauric acid two of 0.5 part. In the first reactor, add 9 parts of Virahols, continue reaction 1h; It is warming up to 80 DEG C, sloughs unnecessary Virahol, be cooled to 60 DEG C, obtain base polyurethane prepolymer for use as A.
The polytetrahydrofuran of 80 parts is added and the molecular weight of 3.5 parts is the hydroxy silicon oil of 2000,100 DEG C of vacuum hydro-extraction 2h in the 2nd reactor; It is cooled to 50 DEG C, adds the isophorone diisocyanate of 16.5 parts and the positive fourth tin of two lauric acid two of 0.1 part. In the 2nd reactor, add two hydroxymethyl propionic acids of 1 part, continue reaction 1h; It is cooled to 60 DEG C, adds 0.76 part of triethylamine, obtain base polyurethane prepolymer for use as B.
50 parts of base polyurethane prepolymer for use as A and 50 part of base polyurethane prepolymer for use as B are mixed with the mass ratio of 1:1. In the mixed system that base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B is formed, add the aqueous solution that molecular weight is the water formation of the polyvinyl alcohol 8 parts of 1788, OP-10 and 272.65 part of 8 parts, dispersed with stirring 30min, adding the diethylenetriamine of 0.85 part again in mixed system, presetting solid content in the present embodiment is 30%.
In the present embodiment, in the first reactor, the mol ratio of isocyano and hydroxyl is 4.5; In 2nd reactor, the ratio of the summation of isocyano and hydroxyl is 1.51.
Carrying out test experiments respectively for the product obtained in the various embodiments described above below, the test event of test experiments comprises: solid content, pH value, apparent, initial viscosity, static 24h mobility, recover viscosity, the ratio (hereinafter referred to as " change ratio ") changing base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B, submissive sense, fine and smooth sense and smooth feeling. Wherein, solid content, pH value, the apparent attribute for characterizing product; Initial viscosity, static 24h mobility, recovery viscosity, change ratio are for characterizing the thixotropic property of product; Submissive sense, fine and smooth sense and smooth feeling are then for characterizing the touch feeling after product film, and test experiments result is as shown in table 1 below:
Table 1
Wherein, the testing method of solid content is with reference to international standard ISO3251 " non-volatile matter of paint and varnish and the paint and varnish mensuration of the non-volatile matter of paint base ".
PH value uses pH test paper to test.
Apparent estimated by people's eye.
Initial viscosity is test with reference to U.S. ASTMD2196 " by the rheological of rotary viscosity design determining non-Newtonian material " after being cooled to room temperature after dispersion discharging.
Static 24h mobility, refers to after at room temperature products therefrom is left standstill 24h, sees if there is viscosity and obviously increase or whether just have mobility.
Recover viscosity to refer to, give and leave standstill the certain shearing of the product after 24h, rock or the reactive force such as stirring, afterwards tested viscosity again.
Submissive sense, fine and smooth sense and smooth feeling are by touching the feel after product film, concrete film be at 65 DEG C, toast 20min after, with hand go touch to see whether have submissive (elasticity sense, fine hair sense or soft feel(ing)), fine and smooth sense, smooth feeling etc.
By above-mentioned test result it will be seen that the polyurethane dispersions obtained by the preparation method of high thixotroping aqueous polyurethane dispersion by the soft feeling coating of the present invention not only has good soft feeling, there is certain intensity simultaneously. In addition, above-mentioned polyurethane dispersions also has thixotropy.
Wherein, when thixotropy refers to that object (such as coating) is subject to shearing, denseness diminishes, and when stopping shearing, denseness increases again; Or when being subject to shearing, denseness becomes big, when stopping shearing, the character that denseness diminishes again. " shear shinning " is called for short for the former, " shearing retrogradation " is called for short for the latter.
If the dispersion obtained by the preparation method of the present invention is as possessed the thixotropy of " shear shinning ", namely time not no, system has higher viscosity, even not there is mobility, stir in time using and revert to again the low state of viscosity, so the storage of dispersion will be had permanent stabilization.
Above-mentioned test result confirms that the product obtained by the various embodiments described above has the thixotropy of " shear shinning " really, and above-mentioned thixotropy does not obtain by adding expensive thixotroping auxiliary agent.
In sum, the dispersion that the soft feeling coating of the present invention is prepared by the preparation method of high thixotroping aqueous polyurethane dispersion not only has strong Flexible, and tack, the intensity after film all obtains comprehensive improvement.
Meanwhile, there is dispersion that the preparation method of the present invention obtains with the use of adding appropriate polyamine as chainextender so that dispersion has high thixotropic, has greatly saved the cost being added thickening material, anti-sedimentation agent and thixotropic agent for improving storage stability.
To those skilled in the art, it is clear that the invention is not restricted to the details of above-mentioned one exemplary embodiment, and when not deviating from spirit or the essential characteristic of the present invention, it is possible to realize the present invention in other specific forms. Therefore, no matter from which point, embodiment all should be regarded as exemplary, and right and wrong are restrictive, the scope of the present invention is limited by claims instead of above-mentioned explanation, it is intended that all changes in the implication of the equivalent important document dropping on claim and scope included in the present invention. Any Reference numeral in claim should be considered as the claim involved by limiting.
In addition, it is to be understood that, although this specification sheets is described according to enforcement mode, but not each enforcement mode only comprises an independent technical scheme, this kind of narrating mode of specification sheets is only for clarity sake, those skilled in the art should by specification sheets integrally, and the technical scheme in each embodiment through suitable conjunction, can also form other enforcement modes that it will be appreciated by those skilled in the art that.
Claims (16)
1. the soft feeling coating preparation method of high thixotroping aqueous polyurethane dispersion, it is characterised in that, described preparation method comprises the steps, in following steps, part number of material is in mass parts:
S1. in the first reactor, 70��90 parts of polyether Glycols are added, dehydration; Cooling, then add the vulcabond of 10��30 parts and the catalyzer of 0.1��1 part;
S2. in the first reactor, add the small molecular alcohol of excessive single functionality, continue reaction;Heating up, slough unnecessary small molecular alcohol, cooling, obtains base polyurethane prepolymer for use as A;
S3. in the 2nd reactor, the polymer polyatomic alcohol of 30��80 parts is added, dehydration; Cooling, adds the vulcabond of 20��70 parts and the catalyzer of 0.1��1 part;
S4. in the 2nd reactor, add the unit molecule dibasic alcohol containing carboxyl of 1��6 part, continue reaction; Cooling, adds neutralizing agent, obtains base polyurethane prepolymer for use as B;
S5. base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B is mixed with the mass ratio of 1:3��2:1;
S6. the solute adding 5��30 parts in the mixed system of base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B formation is the aqueous solution that emulsifying agent or protective colloid are formed, dispersion, then adds polyamine in mixed system, obtains target product.
2. the soft feeling coating according to claim 1 preparation method of high thixotroping aqueous polyurethane dispersion, it is characterised in that, in S1, described polyether Glycols comprises the one in polyoxyethylene glycol, polypropylene glycol, polytetrahydrofuran diol or two or more.
3. the soft feeling coating according to claim 1 and 2 preparation method of high thixotroping aqueous polyurethane dispersion, it is characterised in that, in S1, the scope of the molecular weight of described polyether Glycols is 2000��8000.
4. the soft feeling coating according to claim 1 preparation method of high thixotroping aqueous polyurethane dispersion, it is characterized in that, in S1 and S3, described vulcabond is a kind of in isophorone diisocyanate, hexamethylene diisocyanate or both combinations.
5. the soft feeling coating according to claim 1 preparation method of high thixotroping aqueous polyurethane dispersion, it is characterised in that, in S1 and S3, described catalyzer is tertiary amine catalyst, organic tin catalyzer or organo-bismuth class catalyzer.
6. the soft feeling coating according to claim 1 preparation method of high thixotroping aqueous polyurethane dispersion, it is characterised in that, described S1 specifically comprises: add 70��90 parts of polyether Glycols in the first reactor, vacuum hydro-extraction 2h under at least 100 DEG C of conditions; It is cooled to 50��90 DEG C, then adds the vulcabond of 10��30 parts and the catalyzer of 0.1��1 part, reaction 2��5h.
7. the soft feeling coating according to claim 1 preparation method of high thixotroping aqueous polyurethane dispersion, it is characterized in that, in S2, described small molecular alcohol is selected from methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol mono-ether, ethylene glycol ester, propylene glycol monoether, propylene glycol monoester, glycerol diether.
8. the soft feeling coating according to claim 1 preparation method of high thixotroping aqueous polyurethane dispersion, it is characterised in that, described S2 specifically comprises: the small molecular alcohol adding excessive single functionality in the first reactor, continues to react at least 1h; Being warming up at least 80 DEG C, vacuum sloughs unnecessary small molecular alcohol, is cooled to 60 DEG C, obtains base polyurethane prepolymer for use as A.
9. the soft feeling coating according to claim 1 preparation method of high thixotroping aqueous polyurethane dispersion, it is characterised in that, in S3, polymer polyatomic alcohol is a kind of in polyether polyol and polyester polyol or both combinations.
10. the soft feeling coating according to claim 1 preparation method of high thixotroping aqueous polyurethane dispersion, it is characterized in that, described S3 specifically comprises: the polymer polyatomic alcohol adding 30��80 parts in the 2nd reactor, vacuum hydro-extraction 2h under at least 100 DEG C of conditions;It is cooled to 50��90 DEG C, then adds the vulcabond of 20��70 parts and the catalyzer of 0.1��1 part, reaction 2h.
The 11. soft feeling coatings according to claim 1 preparation method of high thixotroping aqueous polyurethane dispersion, it is characterised in that, in S4, the described unit molecule dibasic alcohol containing carboxyl is two hydroxymethyl propionic acid and the one in two hydroxymethylbutyrate or the two combination.
The 12. soft feeling coatings according to claim 1 preparation method of high thixotroping aqueous polyurethane dispersion, it is characterised in that, described S4 specifically comprises: the unit molecule dibasic alcohol containing carboxyl adding 1��6 part in the 2nd reactor, continues reaction 1��3h; Being cooled to less than 60 DEG C, add tertiary amine neutralization, obtain base polyurethane prepolymer for use as B, described tertiary amine is a kind of in triethylamine and trolamine or both combinations.
The 13. soft feeling coatings according to claim 1 preparation method of high thixotroping aqueous polyurethane dispersion, it is characterized in that, when base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B is mixed by described S5, also comprise and add acetone in the mixed system of base polyurethane prepolymer for use as A and base polyurethane prepolymer for use as B formation.
The 14. soft feeling coatings according to claim 1 preparation method of high thixotroping aqueous polyurethane dispersion; it is characterized in that; in S6, described emulsifying agent and protective colloid are anionic emulsifier, cationic emulsifier, zwitter-ion emulsifying agent, nonionic emulsifying agent.
The 15. soft feeling coatings according to claim 1 preparation method of high thixotroping aqueous polyurethane dispersion, it is characterised in that, in S6, polyamine is the one in diethylenetriamine and triethylene tetramine or the two combination.
16. 1 kinds of soft feeling coatings are with high thixotroping aqueous polyurethane dispersion, it is characterised in that, described soft feeling coating obtains according to the described preparation method of the arbitrary item of claim 1��15 with high thixotroping aqueous polyurethane dispersion.
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