CN101161701A - Polyester water dispersion used as automobile paint and preparation method thereof - Google Patents
Polyester water dispersion used as automobile paint and preparation method thereof Download PDFInfo
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- CN101161701A CN101161701A CNA200710028976XA CN200710028976A CN101161701A CN 101161701 A CN101161701 A CN 101161701A CN A200710028976X A CNA200710028976X A CN A200710028976XA CN 200710028976 A CN200710028976 A CN 200710028976A CN 101161701 A CN101161701 A CN 101161701A
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Abstract
The present invention provides a polyester-water dispersion with a low acid number and a high molecular weight which can be used as painting on the automobile, wherein the water dispersion comprises A) polyester resin which can be dispersed by water, B) neutralizer and C) water. The invention also discloses a preparation method of the polyester dispersion. The polyester-water dispersion has excellent storage stability, and the painting combination which is compounded with other components such as curing agent can be used for multilayer coating, especially for the painting on the automobile to obtain a paint film with an excellent water resistance and anti-stricken performance.
Description
Technical field
The present invention relates to a kind of low acid number, high-molecular weight is as painted polyester water dispersion in the automobile, filming that this polyester water dispersion forms has the excellent comprehensive performance, can be widely used in the application of various bodies of a motor car, the invention still further relates to the preparation method of this polyester water dispersion.
Background technology
Along with the idea of environment protection is rooted in the hearts of the people day by day, restriction volatile thing quantity discharged (VOC) has become rules in succession in various countries in recent years.Existing solvent based coating product and supporting coating process have been run counter to the requirement of Sustainable development on the market.
Vibrin has good performance as filmogen, and for the application of various base materials, its paint film has weather-proof, anti-solvent, characteristics such as strong adhesion.Therefore, from the angle of environment protection and restriction VOC quantity discharged, the water dispersible polyester cold coating has good development prospect.
The body of a motor car coating is a multilayer system, generally includes the electrophoretic deposition prime coat, floating coat, and top coat layer etc., wherein middle japanning can increase the sticking power of priming paint and finish paint, possesses certain rigidity and snappiness, provides the anti-stone of filming to hit performance.Usually, hit performance in order to improve anti-stone, a kind of simple effective method is exactly the molecular weight that improves resin.Yet the raising of molecular weight means the rising of resin viscosity, thereby needs to use more solvent.
Existing general middle enamelling process is that use solvent based coating resin and terpolycyantoamino-formaldehyde resin or other solidifying agent obtain suitable the filming of performance as filmogen behind the baking-curing.Yet in large quantities with an organic solvent, do not meet the requirement of restriction VOC quantity discharged, have the healthy of disaster hidden-trouble, harm workman, particularly ecotope is caused irreversible destruction.
European patent EP 1285937A2 discloses a kind of water dispersible polyester resin, adopt blocked polyisocyanates as solidifying agent, obtain anti-stone after the curing and hit filming of excellent property, yet this polyester dispersion liquid has too high acid number, and residual carboxyl causes adverse influence to the water-fast salt spray resistance of filming.
Chinese patent CN 1549849A discloses a kind of low viscous anti-rubble and has impacted the water dispersible polyester cold coating, and organic solvent content is less than 5%, but acid number influences the water resistance of filming equally up to 40-50.
Summary of the invention
The polyester water dispersion that an object of the present invention is to provide a kind of low acid number, high molecular and have excellent storage stability, and can cooperate with other compositions, have good water-fast and solvent resistance behind the film-forming, it is strong that sticking power and anti-stone hit ability.
Second purpose of the present invention is the preparation method that a kind of this polyester water dispersion will be provided.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of as painted polyester water dispersion in the automobile, it is characterized in that this dispersion includes (A) water and can disperse vibrin, (B) neutralizing agent and (C) water, described polyester resin is that one or more polyprotonic acids and one or more polyvalent alcohols are mixed, carry out melt polycondensation reaction, introduce hydrophilic radical to the polyester molecule chain in the reaction later stage, reaction finishes the polymkeric substance that the back adds one or more organic solvent dissolution gained, its molecular weight is between 4000～8000, hydroxyl value is lower than 60mg KOH/g, acid number is between 15～35mg KOH/g, and mean particle size is less than 500nm.
40 ℃ of following viscosity of this dispersion are lower than 20mPaS, and the content of organic solvent is less than 5%.
Polycarboxylic acid of the present invention can be one or more in terephthalic acid, m-phthalic acid, phthalic acid, phthalic anhydride, trimellitic acid, the trimellitic acid 1,2-anhydride, or 1 in the aliphatic carboxylic acid, one or more in 4-cyclohexane dicarboxylic acid, Succinic Acid, hexanodioic acid, nonane diacid, sebacic acid, the fumaric acid; The polyvalent alcohol polyvalent alcohol is ethylene glycol, propylene glycol, 1,3 butylene glycol, glycol ether, dipropylene glycol, 1,4 cyclohexane dimethanol, 1, ammediol, 1, one or more in 6-hexylene glycol, the neopentyl glycol.
Contain at least 50% aromatic series polycarboxylic acid in the above-mentioned polyprotonic acid component in mole, contain at least 60% ethylene glycol and/or neopentyl glycol in the polyol component in mole.
The water that the present invention adopts can disperse vibrin have enough be neutralized formation water-dispersion salt-the COOH group.
The material of neutralizing agent is NaOH, KOH, ammoniacal liquor, diethylamine, triethylamine, diethanolamine or dimethylethanolamine.
Also include solidifying agent in this dispersion, described solidifying agent is blocked isocyanate or aminoresin.
Above-mentioned preparation method as painted polyester water dispersion in the automobile, include following steps: adopt progressively polymeric method, the preparation high-molecular weight has enough-vibrin of COOH group, this molecular weight of polyesters is between 4000～8000, acid number is between 15～35mgKOH/g, and hydroxyl value is lower than 60mg KOH/g; (A) is dissolved in the organic solvent with polyester, adds neutralizing agent and is neutralized to necessary degree of neutralization; The polyester liquid that obtains is mixed with water, form polyester/solvent/water ternary blends, carry out phase reversion self-emulsifying process, and extract organic solvent being lower than under 60 ℃ the temperature.
In polymerization process, can use polycondensation catalyst in case of necessity, described catalyzer is organic tin, titanate ester or weisspiessglanz compounds.
Below be the optimal technical solution that the present invention adopts:
Vibrin (A) can be dispersed in water (C) medium, does not need to use tensio-active agent.The acid number of vibrin of the present invention more than or equal to 15mg KOH/g less than 35mgKOH/g, if acid number greater than 35mg KOH/g, water-resistance property of coating can descend.When acid number is lower than 15mg KOH/g, be difficult to form the water dispersion of homogeneous.Vibrin comprises a certain amount of hydroxy functional group, and for being unlikely to influence water-resistance property of coating, hydroxyl value should be lower than 60mg KOH/g, is preferably 30～50mg KOH/g.
The vibrin number-average molecular weight is preferably 5000～7000 between 4000～8000, when molecular weight is lower than 4000, be difficult to obtain better comprehensive performance, and molecular weight is not easy to obtain the water dispersion of good storage stability greater than 8000 or when bigger.Have no particular limits for second-order transition temperature, but, be good between-20 ℃～80 ℃ from the car paint application requiring.
Vibrin of the present invention (A) is synthetic by the component of following necessity: polyprotonic acid (a
1), polyvalent alcohol (a
2), other polyprotonic acids and polyvalent alcohol (a
3).
Polyprotonic acid (a
1) can be in aromatic series polycarboxylic acid such as terephthalic acid, m-phthalic acid, phthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, the HHPA one or more; Can be aliphatic carboxylic acid 1, one or more in 4-cyclohexane dicarboxylic acid, Succinic Acid, hexanodioic acid, nonane diacid, sebacic acid, the fumaric acid.
Polyvalent alcohol (a
2) can be ethylene glycol, propylene glycol, 1,3 butylene glycol, glycol ether, dipropylene glycol, 1,4 cyclohexane dimethanol, 1, ammediol, 1, one or more in 6-hexylene glycol, the neopentyl glycol.
Other polyprotonic acids and polyvalent alcohol (a
3) comprise trimellitic acid 1,2-anhydride, dimethylol propionic acid, dimethylolpropionic acid, TriMethylolPropane(TMP), 6-caprolactone etc.
Especially, polyprotonic acid (a
1) in the molar percentage at least 50% of aromatic series polyprotonic acid, be lower than 50% and can reduce hardness and scratch resistant performance.Polyvalent alcohol (a
2) in the molar percentage of ethylene glycol and neopentyl glycol be at least 60%, be lower than 60% and can reduce water-fast and chemical resistance.According to cost performance, preferred use terephthalic acid and m-phthalic acid in the aromatic series polyprotonic acid, and the molar percentage of shared aromatic series polyprotonic acid is advisable greater than 60%.
May comprise that also a kind of molar content is no more than 5% three-functionality-degree or the more polyvalent alcohol of high functionality, for example glycerol, TriMethylolPropane(TMP), tetramethylolmethane etc.
Vibrin can carry out the polycondensation preparation by one or more polyprotonic acids and one or more polyvalent alcohols under the processing condition of knowing; the technology that the present invention adopts is: nitrogen protection; under 180～260 ℃; carry out esterification 3～7h; drop into polycondensation catalyst subsequently; use vaccum-pumping equipment to extract small-molecule substances such as air, water in the system, carry out polycondensation, reach required molecular weight up to polymkeric substance.
According to circumstances, may need to use polycondensation catalyst, catalyzer commonly used comprises organic tin, metatitanic acid class, antimony compounds etc.
In the polycondensation later stage, add a kind of polyprotonic acid or polyol component and under nitrogen protection, carry out depolymerization reaction to obtain needed acid number or hydroxyl value.
The polyprotonic acid that is used for depolymerization reaction is preferably the aromatic series polyprotonic acid, for example aromatic acid (terephthalic acid, m-phthalic acid, phthalic anhydride) and aromatic series polyprotonic acid trimellitic acid (acid anhydride).
The polyvalent alcohol that is used for depolymerization reaction is preferably neopentyl glycol, ethylene glycol etc.
During small-molecule substance such as air, water, the system internal pressure is controlled at 1000Pa or lower in the system of extracting.
" depolymerization " method is a kind of effective control vibrin molecular weight and the polymerization means of regulating polyester functional group, for example, if want the higher vibrin of synthetic molecular weight, under polymerization degree condition with higher, molecular weight is difficult to obtain effective control, therefore, adds an amount of terephthalic acid in the polymerization later stage, synchronous depolymerization and polycondensation be can cause, thereby a suitable acid number and molecular weight provided for the vibrin that obtains at last.
Reaction principle is as follows:
(1) acidolysis reaction takes place down in high temperature, has introduced-the COOH group, causes the polymerization degree to reduce simultaneously.
(2) polycondensation taking place, keeps the polyester relative molecular weight.
Neutralizing agent (B)
Polyester water dispersion of the present invention need use a kind of neutralizing agent, neutralizing agent can in and the carboxyl functional group of vibrin produce the carboxyl negative ion, mutual repulsion between these ions makes vibrin can keep certain dispersion particle diameter, thereby obtains stable water dispersion.
Can include but not limited to NaOH, KOH, ammoniacal liquor, diethylamine, triethylamine, diethanolamine, dimethylethanolamine etc. as the material of neutralizing agent.
As long as can guarantee that water dispersion of the present invention can have satisfactory dispersion stabilization and storage stability, the consumption of neutralizing agent has no particular limits, and adding the amount of substance of neutralizing agent and the ratio of the contained carboxyl of polyester is 60%～100%.
The water that comprises in the dispersion (C) is not particularly limited equally, distilled water, ion exchanged water, tap water, process waters etc. can use, the consumption of water account for dispersion 40% or more, be lower than 40%, may be difficult to form water dispersion.
An importance of the present invention, the system of being carried out a phase reversion from process, change the O/W type into by w/o type, form stable low viscosity emulsion and do not need to add tensio-active agent.
" phase reversion " of the present invention is meant that adds a process that surpasses the water of organic solvent amount in this system in being dissolved with the organic solution system of vibrin, thereby can make system change over O/W emulsion dispersion phase mutually from organic solution.
This process be divided into three the step carry out.The first step, vibrin at first are dissolved in one or more organic solvents, and in this step, vibrin shared percentage ratio in solution is 30～50%.Second step added a certain amount of neutralizing agent and water, and under certain stir speed (S.S.), controlled temperature is no more than 40 ℃, carries out phase reversion self-emulsifying process, and the quality of the water of adding and organic solvent mass ratio are 2: 1～5: 1.In the 3rd step, controlled temperature is no more than 60 ℃, and decompression extracts organic solvent, is lower than 5% up to system solvent quality content.
The employed organic solvent of dissolved polyester can be the various widely used organic solvents of knowing, and comprises ketones solvent, aromatic hydrocarbon solvent, ether solvent, alcoholic solvent, esters solvent etc.Typical ketones solvent comprises acetone, methylethylketone, propione, 2 pentanone, 4-methyl-2 pentanone, pimelinketone, cyclopentanone etc.Typical aromatic hydrocarbon solvent comprises benzene,toluene,xylene etc.Typical ether solvent comprises dioxane, tetrahydrofuran (THF) etc.Typical alcoholic solvent comprises methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol, hexanol, hexalin etc.Typical esters solvent comprises ethyl acetate, propyl acetate, isopropyl acetate, butylacetate, isobutyl acetate, methyl propionate, ethyl propionate etc.
The equipment that is used to extract organic solvent is not particularly limited.When after phase reversion self-emulsifying process, extracting organic solvent, may cause a part of water and the neutralizing agent that has neither part nor lot in effect to be extracted simultaneously.
Solidifying agent (D)
When solidifying agent is aminoresin, at high temperature, the hydroxyl reaction on its methoxyl group and the vibrin molecular chain and crosslinking curing, when solidifying agent was blocked isocyanate, hydroxyl on-NCO group and the polyester molecule chain and carboxyl reaction took place crosslinked and solidify.Solidifying agent can adopt melamine resin such as cmyel 303, cmyel350 (please indicate chemical name) etc.Also can adopt blocked isocyanate such as isophorone diisocyanate (IPDI), trimerization vulcabond (HDI) etc.
Solidification value is generally more than 100 ℃, particularly preferably in solidifying under 130～150 ℃ the temperature.The quality percentage that solidifying agent accounts for total coating resin component is no more than 50%, is preferably 10～30%.
Solidifying agent should add before pigment and the interpolation of other auxiliary agents, and used high speed dispersor to disperse 5～10min, and the adjustment rotating speed is 600～1000r/min.
The application method of polyester water dispersion is as follows:
Polyester water dispersion of the present invention has excellent film forming properties, can form homogeneous successive resin coating film on multiple base material, and the system film can adopt the whole bag of tricks of knowing.
Polyester water dispersion of the present invention may need to comprise some auxiliary agents, colloid protective agent, pigment etc., cooperates preparation aqueous automobile intermediate layer coating composition with an amount of solidifying agent.
Required auxiliary agent comprises anti-settling agent, flow agent, defoamer, detonation suppressor, rheology control agent, pigment dispersing agent, ultraviolet absorbers, wetting agent etc.
Required colloid protective agent comprises polyvinyl alcohol, carboxy cellulose, Natvosol, hydroxypropylcellulose, treated starch, Polyvinylpyrolidone (PVP), polyacrylic acid, some vinyl polymers etc.
Polyester water dispersion and various auxiliary agent, solidifying agent, pigment cooperate, use know join the lacquer method, be coated with paint coating composition can form excellent performances in several ways respectively with priming paint and finish paint etc. compound coating in the aqueous automobile that obtains.
General three sprays, the three baking technologies (3C3B) that adopt of orthodox car multilayer complex films are carried out, and concrete steps are:
In the process polishing, pickling applies one deck electrophoretic primer, baking-curing on the metal substrate of phosphatization;
On priming paint, apply in one deck waterborne polyester of the present invention and paint baking-curing;
Apply one deck finish paint again, baking-curing.
Aqueous automobile intermediate layer coating composition of the present invention can adopt three sprays, two baking (3C2B) technologies, and concrete steps are:
In the process polishing, pickling applies one deck electrophoretic primer, baking-curing on the metal substrate of phosphatization;
On priming paint, apply in one deck waterborne polyester of the present invention and paint flash distillation 3min under 80 ℃ of temperature;
Apply one deck finish paint again, baking-curing.
The invention has the beneficial effects as follows: characteristics of japanning coating composition in of the present invention, be that vibrin molecular weight wherein is higher, hydroxyl value is lower simultaneously, compare with the vibrin of common lower molecular weight, can so also reduce the quantity discharged of VOC in the crosslinking reaction not influencing the more a spot of relatively solidifying agent of use under the film performance situation; Another characteristics of japanning coating composition in of the present invention, be that vibrin wherein has higher second-order transition temperature, during spraying, through after the of short duration flash distillation step, can form more tough and tensile film rapidly, and be not easy to take place " stinging the end " phenomenon afterwards between the top coat layer of Tu Fuing, this is for realize that " wet humidification " spraying coating process is favourable particularly when water-based and solvent based coating are used.Described " stinging the end " is meant that the solvent in the finish paint is softening with the prime paint paint film at an easy rate, even can influence the sticking power of prime paint and orlop or base material, and behind this coating finish paint, the phenomenon that the bottom rhus dermatitis is risen is called " stinging the end "
The present invention is further described below in conjunction with embodiment.
Embodiment
Below in conjunction with embodiment the present invention is further described specifically, but is not limited to the example that provides, as unreceipted, the quantity among the embodiment is mass parts.
Specific embodiment:
Monomer total amount 100phr
Solvent 100～200phr
Neutralizing agent 3～8phr
Water 150～250phr
Solidifying agent 10～30phr
(1) number-average molecular weight
Use GPC to determine number-average molecular weight,, can also obtain the molecular weight distribution situation by gpc analysis.
(2) acid number
Test according to standard GB 6743-86.
(3) hydroxyl value
Test according to national standard HG/T 2709-95.
(4) second-order transition temperature
Use DSC to draw second-order transition temperature (Tg), example weight: 10mg,
10 ℃/min of programed temperature.
(5) solid content
Test according to standard GB 1725-79
(6) storage stability of water dispersion
Get 30ml polyester aqueous dispersions and put into the Glass Containers of a 50ml, placed 60 days down for 25 ℃, observe the dispersion outward appearance whether visible change takes place.
(7) viscosity of water dispersion
Adopt homemade NDJ-79 type rotary viscosity design determining.
(8) film adhesive
Test according to standard GB 1720-1979.
(9) water-resistance property of coating
Put in constant temperature water tank having applied the on-gauge plate of filming, place 120h down for 40 ℃, observe the appearance of filming and change and classification.
(10) solvent resistance of filming
Use acetone to carry out wiping respectively to having applied the on-gauge plate of filming, the wiping number of times when statistics to filming breakage takes place.
(11) salt spray resistance of filming
Using the salt mist experiment machine to simulate various environment tests.
(12) shock resistance of filming
According to standard GB/T 4893.9-1992 test.
1. self-emulsifying vibrin (A) is synthetic, and it is as shown in table 1 to implement prescription.
Example 1 synthesizing polyester resin (A1)
In the four-hole boiling flask that agitator, thermometer, prolong, water trap and nitrogen protection device are housed; press table 1 prescription and add the 84.1g terephthalic acid; 21.0g hexanodioic acid, 14.0g ethylene glycol, 54.9g neopentyl glycol; mix; the oil bath heating slowly is warming up to 160 ℃, after this raises 10 ℃ per half an hour until 240 ℃; carry out esterification process, insulation reaction 5h.Add the 0.18g antimonous oxide, reduce system pressure gradually until being lower than 1000Pa with vaccum-pumping equipment, keep this pressure, reaction 4h removes vaccum-pumping equipment, adds the 6g neopentyl glycol, under this temperature, react 2h, reduce the temperature to 100 ℃, dissolve described polymkeric substance, obtain polyester liquid with the 180g butanone.
With this polyester liquid of 300g and 3.2g N, the N-dimethylethanolamine joins in the flask that prolong and receptor are housed, and is warming up to 30 ℃ under stirring condition, adds the 250g deionized water, adopts vacuum extractor to extract organic solvent, obtains polyester water dispersion.
Example 2 synthesizing polyester resins (A2)
In the four-hole boiling flask that agitator, thermometer, prolong, water trap and nitrogen protection device are housed; press table 1 prescription and add the 80.9g terephthalic acid; 35.2g m-phthalic acid, 17.3g ethylene glycol, 39.3g neopentyl glycol; mix; the oil bath heating slowly is warming up to 160 ℃, after this raises 10 ℃ per half an hour until 240 ℃; carry out esterification process, insulation reaction 5h.Add the 0.38g tetrabutyl titanate, use vaccum-pumping equipment to reduce system pressure gradually until being lower than 1000Pa, keep this pressure, reaction 4h removes vaccum-pumping equipment, adds the 7.3g trimellitic acid 1,2-anhydride, under this temperature, react 2h, reduce the temperature to 100 ℃, dissolve described polymkeric substance, obtain polyester liquid with the 180g butanone.
With this polyester liquid of 300g and 4.2g N, the N-dimethylethanolamine joins in the flask that prolong and receptor are housed, and is warming up to 30 ℃ under stirring condition, adds the 250g deionized water, adopts vacuum extractor to extract organic solvent, obtains polyester water dispersion.
Example 3 synthesizing polyester resins (A3)
In the four-hole boiling flask that agitator, thermometer, prolong, water trap and nitrogen protection device are housed; press table 1 prescription and add the 82.4g terephthalic acid; 34.9g m-phthalic acid, 18.6g ethylene glycol, 40.1g neopentyl glycol; mix; the oil bath heating slowly is warming up to 160 ℃, after this raises 10 ℃ per half an hour until 240 ℃; carry out esterification process, insulation reaction 5h.Add the 0.18g antimonous oxide, use vaccum-pumping equipment to reduce system pressure gradually until being lower than 1000Pa, keep this pressure, reaction 4h removes vaccum-pumping equipment, adds the 4.0g trimellitic acid 1,2-anhydride, under this temperature, react 2h, reduce the temperature to 100 ℃,, obtain polyester liquid with the described polymkeric substance of 180g xylene soluble.
With this polyester liquid of 300g and 4.7g N, the N-dimethylethanolamine joins in the flask that prolong and receptor are housed, and is warming up to 30 ℃ under stirring condition, adds the 250g deionized water, adopts vacuum extractor to extract organic solvent, obtains polyester water dispersion.
Example 4 synthesizing polyester resins (A4)
In the four-hole boiling flask that agitator, thermometer, prolong, water trap and nitrogen protection device are housed; press table 1 prescription and add the 98.6g terephthalic acid; 17.3g m-phthalic acid, 16.3g ethylene glycol, 41.2g neopentyl glycol; mix; the oil bath heating slowly is warming up to 160 ℃, after this raises 10 ℃ per half an hour until 240 ℃; carry out esterification process, insulation reaction 3h.Add the 0.18g antimonous oxide, use vaccum-pumping equipment to reduce system pressure gradually until being lower than 1000Pa, keep this pressure, reaction 4h removes vaccum-pumping equipment, adds the 6.6g 1,3,5-Benzenetricarboxylic acid, under this temperature, react 2h, reduce the temperature to 100 ℃,, obtain polyester liquid with the described polymkeric substance of 180g xylene soluble.
With this polyester liquid of 300g and 5.9g N, the N-dimethylethanolamine joins in the flask that prolong and receptor are housed, and is warming up to 30 ℃ under stirring condition, adds the 250g deionized water, adopts vacuum extractor to extract organic solvent, obtains polyester water dispersion.
Example 5 synthesizing polyester resins (A5)
Synthesis step and prescription carry out depolymerization with example 3 but add the 9.6g trimellitic acid 1,2-anhydride.
The synthesizing formula example and the analytical results of table 1 vibrin
2. painted preparation in the aqueous automobile polyester
Example 1
The dispersion liquid 200g of the Resin A 1 that obtains is poured in the 1L stainless steel vessel, adds the 30g deionized water, 157.5g TiO2, the 52.5g talcum powder, 200g grinds and uses pearl, high speed dispersion 1h, up to fineness less than 10 μ m.Reduce dispersing speed, add 60g Cymel 350 gradually, and regulate total solid content about 55%.
Example 2
The dispersion liquid 200g of the Resin A 2 that obtains is poured in the 1L stainless steel vessel, adds the 30g deionized water, 157.5g TiO2, the 52.5g talcum powder, 200g grinds and uses pearl, high speed dispersion 1h, up to fineness less than 10 μ m.Reduce dispersing speed, add 50g Cymel 350 gradually, and regulate total solid content about 55%.
Example 3
The dispersion liquid 200g of the Resin A 3 that obtains is poured in the 1L stainless steel vessel, adds the 30g deionized water, 157.5g TiO2, the 52.5g talcum powder, 200g grinds and uses pearl, high speed dispersion 1h, up to fineness less than 10 μ m.Reduce dispersing speed, add 37.5g Cymel 350 gradually, and regulate total solid content about 55%.
Example 4
The dispersion liquid 200g of the Resin A 4 that obtains is poured in the 1L stainless steel vessel, adds the 30g deionized water, 157.5g TiO2, the 52.5g talcum powder, 200g grinds and uses pearl, high speed dispersion 1h, up to fineness less than 10 μ m.Reduce dispersing speed, add 37.5g Cymel 350 gradually, and regulate total solid content about 55%.
Example 5
The dispersion liquid 200g of the Resin A 5 that obtains is poured in the 1L stainless steel vessel, adds the 30g deionized water, 157.5g TiO2, the 52.5g talcum powder, 200g grinds and uses pearl, high speed dispersion 1h, up to fineness less than 10 μ m.Reduce dispersing speed, add 37.5g Cymel 350 gradually, and regulate total solid content about 55%.
(annotate: TiO
2: titanium dioxide, trade(brand)name R706, Du Pont produces.Talcum powder: 3000 orders, homemade)
In the aqueous automobile japanning cured paint film character
Japanning adds deionized water respectively and is adjusted to spray viscosity and (is coated with 4 glasss: 20S～25S), place 12h in the aqueous automobile that above-mentioned example is obtained.Adopt the on-gauge plate that has applied electrophoretic primer, spraying 2～3 roads, levelling 10min puts into the baking oven baking-curing.Baking condition: 140 ℃ * 25min.
TPA: terephthalic acid IPA: m-phthalic acid ADA: hexanodioic acid EG: ethylene glycol
NPG: neopentyl glycol
PG:1,3 propylene glycol TMA: trimellitic acid 1,2-anhydride DA
*: refer to depolymerizing agent
Table 2 polyester water dispersion character
Japanning cured paint film performance in the table 3 aqueous automobile polyester
In sum, the high comprehensive performance of the paint film of example 1, example 2 and example 3 reaches the service requirements of painting in the automobile.
Example 4 causes the water tolerance of paint film poor slightly because of the acid number of institute's synthetic vibrin is bigger than normal.And example 5 sides cause the viscosity of water dispersion of vibrin big because of the consumption of trimellitic acid 1,2-anhydride when the synthesizing polyester resin is bigger than normal, the poor water resistance of paint film.
Claims (11)
1. one kind as painted polyester water dispersion in the automobile, it is characterized in that vibrin that this dispersion includes (A) and have automatic emulsifying performance, (B) neutralizing agent and (C) water, described vibrin is that one or more polyprotonic acids and one or more polyvalent alcohols are mixed, carry out melt polycondensation reaction, introduce in the reaction later stage that hydrophilic radical prepares to the polyester molecule chain, the number-average molecular weight of vibrin is higher than 4000, hydroxyl value is lower than 60mgKOH/g, acid number is between 10～30mgKOH/g, with in the neutralizing agent and after add water-dispersion, its median size is less than 500nm.
2. according to claim 1 a kind of as painted polyester water dispersion in the automobile, the content that it is characterized in that described organic solvent is less than 5%.
3. according to claim 1 a kind of as painted polyester water dispersion in the automobile, it is characterized in that described polycarboxylic acid is one or more in terephthalic acid, m-phthalic acid, phthalic acid, phthalic anhydride, trimellitic acid, the trimellitic acid 1,2-anhydride, or 1 in the aliphatic carboxylic acid, one or more in 4-cyclohexane dicarboxylic acid, Succinic Acid, hexanodioic acid, nonane diacid, sebacic acid, the fumaric acid; Described polyvalent alcohol is an ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,3 butylene glycol, glycol ether, dipropylene glycol, 1,4 cyclohexane dimethanol, 1, one or more in 6-hexylene glycol, the neopentyl glycol.
4. according to claim 3 a kind of as painted polyester water dispersion in the automobile, it is characterized in that in the described polyprotonic acid component containing at least 50% aromatic series polycarboxylic acid in mole, contain at least 60% ethylene glycol and/or neopentyl glycol in the polyol component in mole.
5. according to claim 1 a kind of as painted polyester water dispersion in the automobile, it is characterized in that described vibrin have enough be neutralized formation water-soluble salts-the COOH group, make vibrin have automatic emulsifying performance.
6. according to claim 1 a kind of as painted polyester water dispersion in the automobile, it is characterized in that 40 ℃ of following viscosity of this dispersion are lower than 20mPaS.
7. according to claim 1 a kind of as painted polyester water dispersion in the automobile, it is characterized in that described neutralizing agent is NaOH, KOH, ammoniacal liquor, diethylamine, triethylamine, diethanolamine or dimethylethanolamine.
8. according to claim 1 a kind of as painted polyester water dispersion in the automobile, it is characterized in that also including in this dispersion solidifying agent, described solidifying agent is blocked isocyanate or aminoresin.
9. the preparation method as painted polyester water dispersion in the automobile as claimed in claim 1 is characterized in that the method that it comprises the steps: to adopt melt phase polycondensation, and the preparation high-molecular weight has enough-vibrin of COOH group; Vibrin is dissolved in the organic solvent, adds neutralizing agent and be neutralized to necessary degree of neutralization; The polyester resin solution that obtains is mixed with water, and the polyester of formation/solvent/water ternary blends issues looks counter-rotating self-emulsifying action in high-speed stirring, and extracts organic solvent being lower than under 60 ℃ the temperature, makes polyester water dispersion.
10. the preparation method as painted polyester water dispersion in the automobile according to claim 9 is characterized in that having used polycondensation catalyst when polymerization, described catalyzer is organic tin, titanate ester or weisspiessglanz compounds.
11. the preparation method as painted polyester water dispersion in the automobile according to claim 9 is characterized in that adding a kind of polyprotonic acid or polyol component carries out depolymerization reaction in polymerization reaction late stage, to obtain needed acid number or hydroxyl value.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200710028976XA CN101161701A (en) | 2007-06-26 | 2007-06-26 | Polyester water dispersion used as automobile paint and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200710028976XA CN101161701A (en) | 2007-06-26 | 2007-06-26 | Polyester water dispersion used as automobile paint and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101161701A true CN101161701A (en) | 2008-04-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200710028976XA Pending CN101161701A (en) | 2007-06-26 | 2007-06-26 | Polyester water dispersion used as automobile paint and preparation method thereof |
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| CN (1) | CN101161701A (en) |
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