CN103540217B - The double-component aqueous car paint of acrylate resin that a kind of aziridine is crosslinked and its preparation method - Google Patents
The double-component aqueous car paint of acrylate resin that a kind of aziridine is crosslinked and its preparation method Download PDFInfo
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- CN103540217B CN103540217B CN201310465526.2A CN201310465526A CN103540217B CN 103540217 B CN103540217 B CN 103540217B CN 201310465526 A CN201310465526 A CN 201310465526A CN 103540217 B CN103540217 B CN 103540217B
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Abstract
The present invention discloses the double-component aqueous car paint of acrylate resin and its preparation method of a kind of aziridine crosslinking curing. For the preparation of this double-component water paint water-dispersed acrylic ester resin by set of monomers part A, group part B and the mixture of component C in organic cosolvent with radical initiator initiated polymerization, make acrylate resin, then add in amine neutralizing agent and form water dispersion. This water-borne coatings is made up of water-dispersed acrylic ester resin, linking agent aziridine and the mixing of other auxiliary agents, the paint film formed after spraying solidification has high gloss, high rigidity and high-impact performance, have excellent water-resistance, ply adhesion is tight, end material there is is firmly tack, meets the service requirements of car paint.
Description
Technical field
The invention belongs to organic polymer material preparing technical field, it relates to the preparation method of the double-component aqueous car paint of acrylate resin that a kind of aziridine is crosslinked.
Background technology
By State Statistics Bureau's data, from 2000 to 2009, China's coating output increases to about 7,450,000 tons/year from 183.9 ten thousand tons/year, these coating are widely used in the fields such as oil, chemical industry, automobile, boats and ships, metallurgy, electric power, machinofacture, and these fields coating used is all almost solvent based coating, annual organic solvent volatile quantity is up to 2,000,000 tons, and the wasting of resources is roughly equal to hundred million Renminbi more than 110. In the face of the pollution that coating industry is day by day serious, countries in the world have promulgated the use of corresponding regulation limitations solvent based coating in succession. Under the overall background of environment protection, Environmentally friendly coatings, the research and development comprising water-borne coatings, high solid coating, radiation curable coating and powder coating are imperative, and wherein water-borne coatings develops one the most fast.
Aqueous automobile paint is mainly using water as dispersion medium, and containing a small amount of volatile solubility promoter, therefore volatile organic matter (VOC) quantity discharged reduces greatly, reaches the requirement of environmental regulation. But owing to vaporization heat and the surface tension of water causes its velocity of evaporation slower relatively greatly, paint film crosslinking curing temperatures as high 160 DEG C, and paint film easily produces bubble, contracting limit, the stream defect such as extension, the glossiness of paint film, clarity, hardness and water tolerance are also all inferior to solvent based coating. The over-all properties improving water-borne coatings makes it to reach the level of solvent based coating, is the focus of research and development water-borne coatings especially aqueous automobile paint both at home and abroad at present.
Preparing water-borne coatings acrylate resin used, its molecular chain is with wetting ability side bases such as a considerable number of carboxyl, hydroxyls. The group such as carboxyl, hydroxyl is introduced the effect of acrylate resin molecular chain, is to give acrylate resin with water dispersible on the one hand, is for linking agent provides crosslinking reaction group on the other hand. Water soluble acrylic acid ester paint linking agent used is generally water-compatible amino resin linking agent, it is possible to use end-blocking diisocyanate cross-linking agent. Test shows, no matter linking agent used is water-compatible amino resin or end-blocking vulcabond, the water tolerance of its cured paint film is all not good enough, fail to reach the requirement that automobile finishing paint film needs resistance to 40 DEG C of warm water soaking to be greater than 10 days, the consistency that should be aminoresin and end-blocking vulcabond and water-dispersed acrylic ester resin is poor, water-borne coatings disperses bad, cause cross-linking efficiency lower, caused by the carboxyl of paint film and remaining hydroxyl groups amount are relatively big. The present invention provides a kind of feasible in technique, thus the water tolerance of cured paint film is strong less for the cross-linking efficiency height of linking agent and resin, carboxyl and remaining hydroxyl groups amount, the acrylate resin double-component water paint making linking agent with aziridine of glossiness height, other excellent propertys, has important practical value and significant innovative significance.
Summary of the invention
It is an object of the present invention to provide the preparation method of the crosslinked double-component aqueous car paint of acrylate resin of a kind of aziridine. The carboxyl of trifunctional aziridine crosslinker and acrylate resin has higher reactive behavior, just crosslinking reaction can be there is under lower storing temperature, at a higher temperature and under acidic catalyst effect can also with the hydroxyl generation crosslinking reaction of acrylate resin, and very slow with the speed of water reaction. Character according to aziridine crosslinker, the present invention selects the water-soluble solvent of the reactionless effect with aziridine and low-boiling point alcohol kind solvent to carry out acrylic ester monomer and the reaction of styrene monomer free radical solution copolymerization as solubility promoter, synthesize the acrylate resin of molecular chain band carboxyl and hydroxyl, mix with aziridine crosslinker and prepare double-component water paint. Compared with the single-component water-based coating of acrylate resin making linking agent with aminoresin, the acrylate resin double-component water paint making linking agent with aziridine has lower crosslinking curing temperature, aziridine crosslinker is main and the carboxyl of acrylate resin and hydroxyl generation crosslinking reaction, cross-linking efficiency height, paint film has excellent water tolerance because carboxyl and remaining hydroxyl groups amount are few, and there is higher glossiness, hardness and impact resistance, end material bounding force is stronger. The organic solvent content of this kind of novel double-component water paint is few, and VOC emission amount is low, and production environment and air environmental pollution degree is slight, meets the requirement of up-to-date environmental regulation.
The technical scheme that technical solution problem of the present invention adopts is:
The double-component aqueous car paint of acrylate resin that a kind of aziridine is crosslinked, it is characterized in that comprising aziridine crosslinker, water-dispersed acrylic ester resin and universal lacquer auxiliary agent, described water-dispersed acrylic ester resin is by organizing a part A, group part B reacts with component C and becomes, wherein organize the second-order transition temperature height that part A is its homopolymer, the methyl acrylic ester monomer that hardness is high and styrene monomer, group part B is the acrylic ester monomer that second-order transition temperature is low and snappiness is good of its homopolymer, component C comprise containing can make resin have water-dispersible and can with the function monomer of the hydrophilic radical of linking agent generation crosslinked action.
Preferably, the mass ratio of described group of part A, group part B and component C is 30��45:25��40:20��30.
Preferably, described component C be containing can with neutralizing agent neutralization make resin there is water-dispersible and can with one or both in the methacrylic acid of the carboxyl of linking agent generation crosslinked action and vinylformic acid.
Preferably, described component C also comprise the water dispersible that can improve resin and paint film water tolerance can be improved and can with the function monomer of (methyl) esters of acrylic acid of the hydroxyl of linking agent generation crosslinked action and resin viscosity can be reduced, hydroxyl and linking agent generation crosslinked action are provided and can improve resin water tolerance contain in beta-dicarbonyl function monomer one or both.
Preferably, described improve resin water dispersible and paint film water tolerance can be improved and can be one or more in hydroxyethyl methylacrylate, Hydroxyethyl acrylate, Rocryl 410, Propylene glycol monoacrylate with the function monomer of (methyl) esters of acrylic acid of the hydroxyl of linking agent generation crosslinked action; The beta-dicarbonyl function monomer that contains described reducing resin viscosity, provide hydroxyl and linking agent generation crosslinked action and can improving resin water tolerance is one or more in acetoacetoxyethyl methacrylate, diacetone-acryloamide(DAA).
Preferably, described function monomer is methacrylic acid and the wherein one of hydroxyethyl methylacrylate two combination of monomers, methacrylic acid and acetoacetoxyethyl methacrylate two combination of monomers or methacrylic acid and hydroxyethyl methylacrylate and acetoacetoxyethyl methacrylate three combination of monomers; Its batching mass ratio is methacrylic acid: hydroxyethyl methylacrylate=8��12:5��8, methacrylic acid: acetoacetoxyethyl methacrylate=8��12:8��12, methacrylic acid: hydroxyethyl methylacrylate: acetoacetoxyethyl methacrylate=8��12:3��8:3��8.
A preparation method for the double-component aqueous car paint of acrylate that aziridine is crosslinked, comprises the steps:
(1) adding solubility promoter first in the reactor, heat temperature raising in stirring constant temperature, in 105 DEG C, then drip and add group part A, group part B, component C, initiator and chain-transfer agent mixed solution, drip, be incubated 1 hour in 2��4 hours;
(2) then add the initiator solution being dissolved in solubility promoter to system, it is incubated 2��4 hours;
(3) adding neutralizing agent to degree of neutralization is 50%��60%, namely obtains water-dispersed acrylic ester resin;
(4) above-mentioned water-dispersed acrylic ester resin is mixed with aziridine crosslinker, coatings additive(s) and deionized water, namely make the acrylate double-component aqueous car paint crosslinked with aziridine of the present invention.
Preferably, described linking agent is three-functionality-degree aziridine crosslinker, and its consumption is that crosslinked group contained by acrylate resin and carboxyl and hydroxyl equimolar amount add.
Preferably, described synthetic water decentralized acrylate resin organic cosolvent used is one or more mixture of the alcoholic solvent that the boiling points such as two ether solvents of volatile, hypotoxicity and aziridine crosslinker anergy, naphthenic one kind solvent, Virahol, isopropylcarbinol and the trimethyl carbinol are lower, and its consumption is equivalent to the 20%��50% of comonomer quality; Described amine neutralizing agent is not containing reactive hydrogen, with aziridine crosslinker, the tertiary amine of reaction does not occur.
Preferably, described organic solvent is ethylene glycol diethyl ether and isopropyl alcohol mixed solvent; Described neutralizing agent is triethylamine.
Aqueous automobile paint of the present invention is made up of following raw material: water-dispersed acrylic ester resin, aziridine crosslinker and universal lacquer auxiliary agent. Wherein said water-dispersed acrylic ester resin is by (methyl) acrylic ester monomer, styrene monomer and function monomer, organic cosolvent and organic initiators mixing, carry out free radical solution copolymerization reaction, synthesis, containing the acrylate resin of carboxyl and hydroxyl, adds neutralizing agent and namely acrylate resin neutralization is formed water-dispersed acrylic ester resin.
Synthetic water decentralized acrylate resin comonomer used of the present invention is made up of set of monomers part A, group part B and component C. Group part A is the methyl acrylic ester monomer and styrene monomer that its homopolymer Tg height, hardness are high, and described group of part A is selected from the group being made up of following material: methyl methacrylate, isopropyl methacrylate, ��-dimethyl-aminoethylmethacrylate, isobornyl methacrylate, phenyl methacrylate, methacrylic acid benzyl ester, n propyl methacrylate, n-BMA, vinylbenzene; Group part B is the acrylic ester monomer that its homopolymer Tg is low, snappiness is good, and described group of part B is selected from the group being made up of following material: n-butyl acrylate, acrylic acid-2-ethyl cyclohexyl, vinylformic acid n-propyl, vinylformic acid n-octyl, vinylformic acid ester in the positive last of the ten Heavenly stems.
Component C is function monomer. The function monomer that the present invention uses divides three classes. The first kind be containing can with neutralizing agent neutralization make resin have water-dispersible and can with the function monomer of the hydrophilic radical carboxyl of aziridine generation crosslinked action, this kind of function monomer is (alkyl) acrylic monomer, comprise vinylformic acid, methacrylic acid, the mix monomer of ethylacrylic acid wherein one or more; 2nd class be can improve resin water dispersible and improve paint film water resistance and can with the function monomer of (methyl) esters of acrylic acid of the hydroxyl of linking agent generation crosslinked action, this kind of function monomer is hydroxyethyl methylacrylate, Hydroxyethyl acrylate, Rocryl 410, Propylene glycol monoacrylate wherein one or more mix monomer; 3rd class be can reduce resin viscosity, hydroxyl and linking agent generation crosslinked action are provided and improve resin water tolerance contain beta-dicarbonyl function monomer; this kind of function monomer is acetoacetoxyethyl methacrylate and diacetone-acryloamide(DAA); wherein acetoacetyl group has keto-enol tautomer, its enol form isomer hydroxyl.
When acrylic ester synthesizing resin, the throwing material mass ratio of above-mentioned all kinds of monomer is group part A: group part B: component C=30��45:25��40:20��30. The acrylate resin molecular chain formed contains the side base of the enol-type structure of carboxyl, hydroxyl and acetoacetyl.
The copolyreaction of above-mentioned each component monomer mixture carries out in organic cosolvent, it is desired to solubility promoter used is volatile solvent, and can meet following requirement: one is low poison, can be miscible with water; Two is that boiling point is lower, leaves standstill in process volatilizable in spraying and film, and before reaching crosslinking reaction temperature, (about about 100 DEG C) should all be evaporated completely; If three is boiling point higher (> 110 DEG C), can not react with aziridine crosslinker under storing temperature; Four is when being scattered in water by copolymerization product acrylate resin, and this kind solvent can play solubility promoter. This kind solvent mainly single methanol class, two ether class, naphthenic one kind solvent, comprise n-propyl alcohol, Virahol, sec-butyl alcohol, the trimethyl carbinol, ethylene glycol diethyl ether, diethylene glycol diethyl ether, pimelinketone one wherein, or several mixtures. The consumption of organic solvent is the 20%��50% of mix monomer total mass. Wherein optimum solvent is the mixture of ethylene glycol diethyl ether and Virahol.
For neutralize acrylate resin neutralizing agent with not containing reactive hydrogen and hydroxyl, thus not easily occur the tertiary amine of reaction to be good with aziridine crosslinker, comprising xylidine, Diethyl Aniline, Trimethylamine 99, triethylamine, triphenylamine etc., wherein optimum neutralizing agent is triethylamine. In and during acrylic ester resin solution, relatively more suitable taking degree of neutralization as 50%��60%.
Acrylate resin aqueous automobile paint linking agent used provided by the invention is aziridine crosslinker, belong to double-component water paint, after adding aziridine crosslinker, this coating should be finished in 5 hours, and this coating automatically cross-linked reaction slowly can occur and lost efficacy more than 5 hours storage period. Coatings additive(s) comprises the apparent property that flow agent, defoamer etc. can improve paint film.
The synthesizing formula of water-dispersed acrylic ester resin is as shown in table 1, and the formula of the double-component aqueous car paint of acrylate resin that preparation aziridine is crosslinked is as shown in table 2.
The synthesizing formula of table 1 water-dispersed acrylic ester resin
Wherein regulate above-mentioned group of part to being coated with-4 glasss of viscosity 23 �� 1s with deionized water.
The synthesis process of water-dispersed acrylic ester resin provided by the invention is as follows: add organic mixed solvent in the reactor; it is warmed up to 102 DEG C under nitrogen protection; all monomers are mixed with initiator; drip after dissolving in organic mixed solvent; dropwising in 2��4h, insulation 1h, then adds the initiator solution being dissolved in solubility promoter to system; dropwise in 0.5h, insulation 2��4h. Being cooled to 60 DEG C, adding neutralizing agent to degree of neutralization is 50%��60%, namely obtains water-dispersed acrylic ester resin.
Aqueous automobile paint provided by the invention join paint and baking process process as follows: aziridine crosslinker Sac-100 and ethylene glycol diethyl ether are mixed for subsequent use in the ratio of 2:1. Water-dispersed acrylic ester resin and a certain amount of linking agent mixed solution are mixed, then adding defoamer, flow agent, diethylene glycol diethyl ether and deionized water, adjusting viscosity, to being coated with-4 glasss of 23 �� 1s, stirs evenly, leave standstill the bubble that disappears for 10 minutes, with 200 order filter-cloth filterings. Film is by GB GB1727-92 preparation, and tinplate face used is of a size of 25mm �� 120mm, through degreasing, eliminates rust and after bonderizing, adopts spraying method to prepare dark paint film on plate face, spray the double-component aqueous car paint of the present invention on dark paint film. Flat 15 minutes of stream at normal temperatures after spraying, storing temperature is 130 DEG C��140 DEG C, baking time is 30min. Paint film property comprises film thickness, glossiness, hardness, sticking power, flexural strength, shock strength and water tolerance by concerned countries standard test.
The invention has the beneficial effects as follows: the preparation method of the acrylate resin double-component water paint being cross-linked from aziridine provided by the invention, described acrylate resin double-component water paint is the water-dispersed acrylic ester resin by molecular chain band carboxyl and hydroxyl, aziridine crosslinker, with the water-soluble co-solvents of the reactionless activity of aziridine crosslinker such as ethylene glycol diethyl ether, lower boiling water-soluble alcohol kind solvent is such as Virahol, with the low-boiling amine class neutralizing agent of the reactionless activity of aziridine such as triethylamine, deionized water and a small amount of coatings additive(s) Homogeneous phase mixing are formed. this double-component water paint leaves standstill in process in spraying and film, part lower boiling co-solvent is volatilized, when storing temperature raises from room temperature, the carboxyl not neutralized in aziridine and acrylate resin just starts crosslinking reaction at a lower temperature, and the rising with storing temperature, cross-linked speed is accelerated, the rate of volatilization of lower boiling co-solvent is also accelerated, storing temperature rises to about 100 DEG C, the carboxyl not neutralized and the crosslinking reaction degree of aziridine are very high, lower boiling co-solvent is also volatilized substantially completely, along with storing temperature raises further, the carboxylic acid amine salt that carboxyl and amine class neutralizing agent are formed decomposes, precipitate out carboxyl and amine, the latter is volatilized disengaging paint film, at this moment the temperature of reaction of aziridine and hydroxyl has been reached. the carboxyl precipitated out becomes on the one hand the hydroxyl generation crosslinking reaction of an acidic catalyst catalysis aziridine and acrylate resin, another aspect also with aziridine generation crosslinking reaction. as can be seen here, the aziridine crosslinker of this double-component water paint mainly first with the carboxyl of resin after with hydroxyl generation crosslinking reaction, other side reactions are then less, therefore cross-linking efficiency height, carboxyl and the remaining hydroxyl groups amount of paint film are few, cause paint film to have excellent water tolerance and glossiness and other performances, meet the service requirements of automobile overprint coating.
Accompanying drawing explanation
Fig. 1 is the synthetic technology route of the present invention's water-dispersed acrylic ester resin used;
Fig. 2 be the aqueous automobile overprint coating of the present invention join paint technological line;
Fig. 3 is the schematic arrangement of the present invention's aziridine hardener used;
Fig. 4 is the chemical equation of the compound of aziridine and band carboxyl;
Fig. 5 is aziridine and the chemical equation of hydroxyl compound.
Below in conjunction with embodiment, the present invention is further described.
Embodiment
Below in conjunction with embodiment, the present invention is further described in detail, but it is not limited thereto.
Embodiment 1
Table 3 is that embodiment 1 is in function monomer methacrylic acid and function monomer acetoacetoxyethyl methacrylate combine, it is fixed as 10% at acetoacetoxyethyl methacrylate consumption, and the throwing material formula of the consumption progressively increasing methacrylic acid synthetic water decentralized acrylate resin when being 7%, 8%, 9%, 10%, 11% and 14%, its formula numbering is followed successively by 1,2,3,4,5 and 6, has 6 formulas. 6 formulas of embodiment 1 all adopt synthesis process identical as follows.
25 parts of ethylene glycol diethyl ethers and 15 parts of Virahols are added and is equipped with agitator, prolong, in four mouthfuls of flasks of thermometer and oil bath heating unit, under nitrogen protection, it is warming up to 105 DEG C, by the methacrylic acid of formula consumption, methyl methacrylate, vinylbenzene, acetoacetoxyethyl methacrylate, butyl acrylate, Diisopropyl azodicarboxylate and lauryl mercaptan mixed solution constant pressure funnel are dripped in four mouthfuls of flasks, drip in 4h, insulation 1h, remaining Diisopropyl azodicarboxylate is dissolved with 10 parts of ethylene glycol diethyl ethers, then add in four mouthfuls of flasks, insulation 3h, obtain semi-transparent clear acrylate copolymer solution. it is cooled to 60 DEG C, drips and add triethylamine resin solution is neutralized to degree of neutralization is 50%, obtain the water-dispersed acrylic ester resin of water white transparency.
Lacquer man's skill process: all adopt by the water-dispersed acrylic ester resins of embodiment 1 numbering 1,2,3,4,5 with 6 of 6 formula synthesis and identical as follows join paint formula and technological process.
25phr aziridine crosslinker Sac-100 and 12.5phr ethylene glycol diethyl ether are mixed for subsequent use in the ratio of 2:1. 100phr resin and 25phr aziridine crosslinker are mixed with the mixed solution of 12.5phr ethylene glycol diethyl ether, then interpolation 0.12phr defoamer BYK-028,0.12phr flow agent BYK-333,10phr diethylene glycol diethyl ether and about 290phr deionized water, dope viscosity is adjusted to and is coated with-4 glasss of 23 �� 1s, stir evenly, leave standstill the bubble that disappears for 10 minutes, with 200 order filter-cloth filterings, acquisition take aziridine as the acrylate resin double-component water paint of linking agent. Spraying prepared double-component water paint by GB GB1727-92 on the dark paint film of tinplate, film flows flat 15 minutes at normal temperatures, then toasts 30 minutes at 130 DEG C, obtains cured paint film. By every performance of concerned countries standard test cured paint film, wherein the condition determination of water tolerance soaks in the deionized water of 40 DEG C, record loss of gloss, variable color, bubble, wrinkling, come off, time that the phenomenon such as get rusty occurs, the water tolerance of cured paint film is dipped in the water of 40 DEG C with cured paint film occurs that needed for above-mentioned phenomenon, number of days is expressed. As automobile finishing paint film, the performance of its resistance to 40 DEG C of warm water must be greater than 10 days.
Table 4 is that the consumption of methacrylic acid is on the outward appearance of acrylate resin double-component aqueous automobile overprint coating crosslinked with aziridine and the impact of cured paint film performance thereof, the visible increase along with methacrylic acid consumption, the every excellent property of cured paint film and change are little, water tolerance then first improves and reduces afterwards, it is in 9%��11% scope at methacrylic acid consumption, the water tolerance of cured paint film reaches more than 15 days, reach automobile finishing paint film to the requirement of water tolerance, when methacrylic acid consumption is 10%, the over-all properties of cured paint film reaches best level, wherein water tolerance was up to 25 days.
Table 3 embodiment 1 changes the basic recipe of the consumption synthetic water decentralized acrylate resin of methacrylic acid
The relation of table 4 embodiment 1 methacrylic acid consumption and acrylate resin double-component water paint paint film property
Embodiment 2
Table 5 embodiment 2 changes the basic recipe of vinylformic acid consumption synthetic water decentralized acrylate resin
Table 5 is that embodiment 2 is in function monomer methacrylic acid and function monomer acetoacetoxyethyl methacrylate combine, being fixed as 10% at acetoacetoxyethyl methacrylate consumption and progressively increase acrylic acid consumption is 5.5%, 6.5%, 7.5%, 8.5%, 9.5% and 10.5%, the throwing material formula of synthetic water decentralized acrylate resin when the consumption of corresponding minimizing methyl methacrylate simultaneously, its formula numbering is followed successively by 7,8,9,10,11 and 12, has 6 formulas. The synthesis process of each formula is identical.
By the 6 kinds of water-dispersed acrylic ester resins being numbered 7��12 shown in the technological process synthetic table 5 of embodiment 1 synthetic water decentralized acrylate resin, prepare the formula of coating by embodiment 1 and lacquer man's skill process prepares aziridine cross linked acrylic resin double-component aqueous automobile overprint coating and cured paint film thereof.
The relation of table 6 embodiment 2 vinylformic acid consumption and acrylate resin double-component water paint paint film property
Table 6 is that acrylic acid consumption is on the outward appearance of acrylate resin double-component aqueous automobile overprint coating crosslinked with aziridine and the impact of cured paint film performance thereof, the visible increase along with vinylformic acid consumption, the every excellent property of cured paint film and change are little, water tolerance then first improves and reduces afterwards, it is in 7.5%��9.5% scope at vinylformic acid consumption, the water tolerance of cured paint film reaches more than 15 days, reach automobile finishing paint film to the requirement of water tolerance, when vinylformic acid consumption is 8.5%, the over-all properties of cured paint film reaches best level, and wherein water tolerance was up to 22 days.
Embodiment 3
Table 7 embodiment 3 changes the basic recipe of acetoacetoxyethyl methacrylate consumption synthetic water decentralized acrylate resin
Table 7 is that embodiment 3 is in function monomer methacrylic acid and function monomer acetoacetoxyethyl methacrylate combine, the consumption being fixed as 10% at methacrylic acid consumption and progressively increasing acetoacetoxyethyl methacrylate is 7%, 8%, 9%, 10%, 11% and 14%, the throwing material formula of synthetic water decentralized acrylate resin when the consumption of corresponding minimizing methyl methacrylate simultaneously, its formula numbering is followed successively by 13,14,15,16,17 and 18, has 6 formulas. The synthesis process of each formula is identical.
By the 6 kinds of water-dispersed acrylic ester resins being numbered 13��18 shown in the technological process synthetic table 7 of embodiment 1 synthetic water decentralized acrylate resin, prepare the formula of coating by embodiment 1 and lacquer man's skill process prepares aziridine cross linked acrylic resin double-component aqueous automobile overprint coating and cured paint film thereof.
Table 8 is the consumption of embodiment 3 acetoacetoxyethyl methacrylate and the relation of acrylate resin aqueous paint cured paint film performance, the visible increase along with acetoacetoxyethyl methacrylate consumption, the glossiness of paint film, pencil hardness, sticking power, bending property and shock resistance be all in higher level and change little, water tolerance then first improves and decreases afterwards, over-all properties at 10% place's cured paint film reaches optimum, water tolerance reaches maximum value, is 25 days.
The relation of table 8 embodiment 3AAEM consumption and acrylate resin double-component water paint cured paint film performance
Embodiment 4
Table 9 embodiment 4 changes the basic recipe of hydroxyethyl methylacrylate consumption synthetic water decentralized acrylate resin
Table 9 is that embodiment 4 is in function monomer methacrylic acid and function monomer hydroxyethyl methylacrylate combine, the consumption being fixed as 10% at methacrylic acid consumption and progressively increasing hydroxyethyl methylacrylate is 5%, 6%, 7%, 8% and 10%, the throwing material formula of synthetic water decentralized acrylate resin when the consumption of corresponding minimizing methyl methacrylate simultaneously, its formula numbering is followed successively by 19,20,20,22 and 23, has 5 formulas. The synthesis process of each formula is identical.
By the 5 kinds of water-dispersed acrylic ester resins being numbered 19��23 shown in the technological process synthetic table 9 of embodiment 1 synthetic water decentralized acrylate resin, prepare the formula of coating by embodiment 1 and lacquer man's skill process prepares aziridine cross linked acrylic resin double-component aqueous automobile overprint coating and cured paint film thereof.
Table 10 is the consumption of embodiment 4 hydroxyethyl methylacrylate and the relation of acrylate resin aqueous paint cured paint film performance, the visible increase along with hydroxyethyl methylacrylate consumption, the glossiness of paint film, pencil hardness, sticking power, bending property and shock resistance be all in higher level and change little, water tolerance then first improves and reduces afterwards, over-all properties at 7% place's cured paint film reaches optimum, water tolerance reaches maximum value, is 23 days.
The relation of table 10 embodiment 4 hydroxyethyl methylacrylate consumption and acrylate double-component water paint cured paint film performance
Embodiment 5
Table 11 embodiment 5 changes the basic recipe of Rocryl 410 consumption synthetic water decentralized acrylate resin
Table 11 is that embodiment 5 is in function monomer methacrylic acid and function monomer Rocryl 410 combine, the consumption being fixed as 10% at methacrylic acid consumption and progressively increasing Rocryl 410 is 5%, 6%, 7%, 8% and 10%, the throwing material formula of synthetic water decentralized acrylate resin when the consumption of corresponding minimizing methyl methacrylate simultaneously, its formula numbering is followed successively by 24,25,26,27 and 28, has 5 formulas. The synthesis process of each formula is identical.
By the 5 kinds of water-dispersed acrylic ester resins being numbered 24��28 shown in the technological process synthetic table 11 of embodiment 1 synthetic water decentralized acrylate resin, prepare the formula of coating by embodiment 1 and lacquer man's skill process prepares aziridine cross linked acrylic resin double-component aqueous automobile overprint coating and cured paint film thereof.
Table 12 is the consumption of embodiment 5 Rocryl 410 and the relation of acrylate resin aqueous paint cured paint film performance, the visible increase along with Rocryl 410 consumption, the glossiness of paint film, pencil hardness, sticking power, bending property and shock resistance be all in higher level and change little, water tolerance then first improves and reduces afterwards, over-all properties at 7% place's cured paint film reaches optimum, water tolerance reaches maximum value, is 25 days.
The relation of table 12 embodiment 5 Rocryl 410 consumption and acrylate double-component water paint cured paint film performance
Embodiment 6
Table 13 embodiment 6 changes the basic recipe of AAEM/HEMA proportioning synthetic water decentralized acrylate resin
Table 13 is that embodiment 6 is in function monomer methacrylic acid, function monomer hydroxyethyl methylacrylate and function monomer acetoacetoxyethyl methacrylate combine, the throwing material formula of the water-dispersed acrylic ester resin synthesized when the proportioning that methacrylic acid consumption is fixed as 10% and progressively changes AAEM/HEMA is 2/8,3/7,5/5,7/3 and 8/2, its formula numbering is followed successively by 29,30,31,32 and 33, has 5 formulas. The synthesis process of each formula is identical.
By the 5 kinds of water-dispersed acrylic ester resins being numbered 29��33 shown in the technological process synthetic table 13 of embodiment 1 synthetic water decentralized acrylate resin, prepare the formula of coating by embodiment 1 and lacquer man's skill process prepares aziridine cross linked acrylic resin double-component aqueous automobile overprint coating and cured paint film thereof.
The relation of table 14 embodiment 6AAEM/HEMA proportioning and acrylate resin aqueous paint cured paint film performance
Table 14 is embodiment 6AAEM/HEMA proportioning and the relation of acrylate resin double-component water paint cured paint film performance, the visible change along with AAEM/HEMA proportioning, the glossiness of paint film, pencil hardness, sticking power, bending property and shock resistance be all in higher level and change little, water tolerance also all reaches the service requirements of automobile finishing paint film, the over-all properties being 3/7 place's cured paint film at AAEM/HEMA reaches optimum, water tolerance reaches maximum value, is 32 days.
Embodiment 7
Table 15 embodiment 7 changes the basic recipe of neutralizing agent triethylamine consumption synthetic water decentralized acrylate resin
Table 15 is that embodiment 7 is in function monomer methacrylic acid and function monomer acetoacetoxyethyl methacrylate combine, the basic recipe of synthetic water decentralized acrylate resin when the consumption that the consumption of methacrylic acid and acetoacetoxyethyl methacrylate is all fixed as 10% and progressively increases neutralizing agent triethylamine is 4.70%, 5.87%, 7.10%, 8.22% and 9.40%, its formula numbering is followed successively by 34,35,36,37 and 38, has 5 formulas. The synthesis synthesis process of each formula is identical.
By the 5 kinds of water-dispersed acrylic ester resins being numbered 34��38 shown in the technological process synthetic table 15 of embodiment 1 synthetic water decentralized acrylate resin, prepare the formula of coating by embodiment 1 and lacquer man's skill process prepares aziridine cross linked acrylic resin double-component aqueous automobile overprint coating and cured paint film thereof.
The relation of table 16 embodiment 7 neutralizing agent triethylamine consumption and acrylate resin double-component water paint cured paint film performance
Table 16 is embodiment 7 neutralizing agent triethylamine consumption and the relation of acrylate resin double-component water paint cured paint film performance, the visible increase along with degree of neutralization, the pH value of resin improves gradually, when degree of neutralization is 40%��80%, the pH value of resin is in acid, cured paint film all has excellent glossiness, hardness, sticking power, bending property, impact resistance and water tolerance, and along with the increase of degree of neutralization substantially constant, all reach the service requirements of automobile overprint coating. When triethylamine consumption is 5.87%, the over-all properties of cured paint film reaches optimum, and water tolerance was up to 25 days.
Embodiment 8
The basic recipe of table 17 embodiment 8 synthetic water decentralized acrylate resin
Table 17 is embodiment 8 in function monomer methacrylic acid and function monomer acetoacetoxyethyl methacrylate combine, the basic recipe of synthetic water decentralized acrylate resin when the consumption of methacrylic acid and acetoacetoxyethyl methacrylate is all fixed as 10%.
By water-dispersed acrylic ester resin shown in the technological process synthetic table 17 of embodiment 1 synthetic water decentralized acrylate resin, prepare the formula of coating by embodiment 1 and lacquer man's skill process prepares aziridine cross linked acrylic resin double-component aqueous automobile overprint coating, adopt the solidification value of 115 DEG C, 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C and 140 DEG C to prepare cured paint film respectively. From table 18, when solidification value is 115��140 DEG C, the glossiness of cured paint film, pencil hardness, sticking power, bending property and shock resistance significantly do not change, and all reach excellent level, and water tolerance all reaches good level and improves gradually. After solidification value is higher than 130 DEG C, the water tolerance of cured paint film improves not remarkable. Both can obtain excellent paint film property when solidification value is 130 DEG C, again can save energy, therefore solidification value is advisable with 130 DEG C.
The relation of table 18 solidification value and acrylate double-component water paint cured paint film performance
Note: set time is 30min.
Embodiment 9
By water-dispersed acrylic ester resin shown in the technological process synthetic table 17 of embodiment 1 synthetic water decentralized acrylate resin, prepare the formula of coating by embodiment 1 and lacquer man's skill process prepares aziridine cross linked acrylic resin double-component aqueous automobile overprint coating, adopt prepare cured paint film the set time of 20min, 25min, 30min, 35min, 40min and 45min respectively. From table 19, when being 20min between when solidified, the physical and mechanical properties of cured paint film is better, but water tolerance is very poor, when being 25min��45min between when solidified, glossiness, the bending property shock resistance of cured paint film significantly do not change, and pencil hardness, sticking power and water tolerance progressively rise. Within the set time of 25min��45min, cured paint film all has excellent performance. Between when solidified more than 30 minutes after, crosslinking reaction is tending towards complete, therefore the every performance of paint film is all more excellent. Considering performance and the save energy of cured paint film, set time is advisable with 30min.
The relation of table 19 set time and acrylate resin double-component water paint cured paint film performance
Embodiment 10
By water-dispersed acrylic ester resin shown in the technological process synthetic table 17 of embodiment 1 synthetic water decentralized acrylate resin, prepare the formula of coating by embodiment 1 and lacquer man's skill process prepares aziridine cross linked acrylic resin double-component aqueous automobile overprint coating, investigate respectively coating place 0.5 hour, 1 hour, 2 hours, 3 hours, 4 hours and 5 hours after on the impact of cured paint film performance. From table 20, when coating storage period is 0.5h��5h, the glossiness of cured paint film, pencil hardness, bending property and shock resistance significantly do not change, and water tolerance then declines gradually. This is because cross-linking and curing reaction slowly occurs coating in placement process, placing more of a specified duration, crosslinking degree is more big. When the paint spay-coating having certain crosslinking degree is solidified, crosslinked coating can not again with other coating generation crosslinking reactions, cause the compactness of cured paint film to reduce, the water tolerance of paint film declines. Being 5 hours between when left, every performance of paint film is still in better level, illustrates that the storage period of this dual-component coating the longest is 5 hours after adding aziridine crosslinker.
The relation of table 20 storage period and acrylate resin double-component water paint cured paint film performance
Embodiment 11
Table 21 basic recipe of different types of monomer synthesize water-dispersed acrylic ester resin
The relation of the different types of monomer of table 22 and acrylate resin double-component water paint cured paint film performance
By water-dispersed acrylic ester resin shown in the technological process synthetic table 21 of embodiment 1 synthetic water decentralized acrylate resin, prepare the formula of coating by embodiment 1 and lacquer man's skill process prepares aziridine cross linked acrylic resin double-component aqueous automobile overprint coating, investigate different monomers kind to the impact of cured paint film performance. From table 22, when using different monomers, physical and mechanical properties and the water tolerance of cured paint film all significantly do not change, and are all in higher level, have all reached the service requirements of automobile overprint coating.
Embodiment 12
The basic recipe of table 23 embodiment 12 synthetic water decentralized acrylate resin
By water-dispersed acrylic ester resin shown in the technological process synthetic table 23 of embodiment 1 synthetic water decentralized acrylate resin, the formula of coating is prepared and lacquer man's skill process prepares the single-component water-based automobile overprint coating of amino resin crosslinked acrylate resin by table 24, crosslinking curing temperature is 140 DEG C, and the time is 30min.
The amino resin crosslinked aqueous automobile overprint coating of table 24 join paint basic recipe
The relation of table 25 different monomers kind and the single-component water-based coating lacquer film properties of acrylate resin
Table 25 is the outward appearance of the double-component aqueous automobile overprint coating of different monomers kind and amino resin crosslinked acrylate resin and the impact of cured paint film performance thereof, visible when identical crosslinking curing, it is more or less the same by the physical and mechanical properties of the physical and mechanical properties of amino resin crosslinked solidification gained paint film and aziridine crosslinking curing gained paint film, but obviously it is better than the paint film with amino resin crosslinked solidification gained by the water tolerance of aziridine crosslinking curing gained paint film. This is because with aziridine as linking agent time, the consistency of itself and resin is better, than being easier to be dispersed in resin system, and the viscosity of amino resin crosslinking agent is big, in resin, difficulties in dispersion, dispersed homogeneous degree are poor, so when making linking agent with aziridine, the crosslinking degree of gained cured paint film is higher, paint film property is also more excellent.
Claims (6)
1. the double-component aqueous car paint of acrylate resin being cross-linked with aziridine, it is characterized in that comprising aziridine crosslinker, water-dispersed acrylic ester resin and universal lacquer auxiliary agent, described water-dispersed acrylic ester resin by organizing a part A, group part B react with component C, wherein group part A is the methyl acrylic ester monomer and styrene monomer that the second-order transition temperature height of its homopolymer, hardness are high; Group part B is the acrylic ester monomer that second-order transition temperature is low and snappiness is good of its homopolymer; Component C comprise containing can make resin have water-dispersible and can with the function monomer of the hydrophilic radical of linking agent generation crosslinked action; Described aziridine crosslinker is three-functionality-degree aziridine crosslinker; The mass ratio of described group of part A, group part B and component C is 30��45:25��40:20��30;
Described group of part A is selected from the group being made up of following material: methyl methacrylate, isopropyl methacrylate, ��-dimethyl-aminoethylmethacrylate, isobornyl methacrylate, phenyl methacrylate, methacrylic acid benzyl ester, n propyl methacrylate, n-BMA, vinylbenzene, and organizes in part A containing vinylbenzene; Described group of part B is selected from the group being made up of following material: n-butyl acrylate, acrylic acid-2-ethyl cyclohexyl, vinylformic acid n-propyl, vinylformic acid n-octyl, vinylformic acid ester in the positive last of the ten Heavenly stems;
Described function monomer is methacrylic acid and the wherein one of hydroxyethyl methylacrylate two combination of monomers, methacrylic acid and acetoacetoxyethyl methacrylate two combination of monomers or methacrylic acid and hydroxyethyl methylacrylate and acetoacetoxyethyl methacrylate three combination of monomers; Its batching mass ratio is respectively methacrylic acid: hydroxyethyl methylacrylate=8��12:5��8, methacrylic acid: acetoacetoxyethyl methacrylate=8��12:8��12, methacrylic acid: hydroxyethyl methylacrylate: acetoacetoxyethyl methacrylate=8��12:3��8:3��8;
Synthetic water decentralized acrylate resin organic cosolvent used is the mixed solvent of ethylene glycol diethyl ether and Virahol, and neutralizing agent used is triethylamine.
2. the double-component aqueous car paint of acrylate resin that a kind of aziridine is crosslinked according to claim 1, it is characterised in that described component C also comprise the water dispersible that can improve resin and paint film water tolerance can be improved and can with the function monomer of (methyl) esters of acrylic acid of the hydroxyl of linking agent generation crosslinked action and resin viscosity can be reduced, hydroxyl and linking agent generation crosslinked action are provided and can improve resin water tolerance contain in beta-dicarbonyl function monomer one or both.
3. the double-component aqueous car paint of acrylate resin that a kind of aziridine according to claim 2 is crosslinked, it is characterised in that described improve resin water dispersible and paint film water tolerance can be improved and can be one or more in hydroxyethyl methylacrylate, Hydroxyethyl acrylate, Rocryl 410, Propylene glycol monoacrylate with the function monomer of (methyl) esters of acrylic acid of the hydroxyl of linking agent generation crosslinked action; The beta-dicarbonyl function monomer that contains described reducing resin viscosity, provide hydroxyl and linking agent generation crosslinked action and can improving resin water tolerance is one or more in acetoacetoxyethyl methacrylate, diacetone-acryloamide(DAA).
4. the double-component aqueous car paint of acrylate resin that a kind of aziridine according to claim 1 is crosslinked, it is characterised in that described synthetic water decentralized acrylate resin organic cosolvent consumption used is equivalent to the 20%��50% of comonomer quality.
5. the preparation method of the double-component aqueous car paint of acrylate resin that a kind of aziridine according to claim 1 is crosslinked, comprises the steps:
(1) adding solubility promoter first in the reactor, heat temperature raising in stirring constant temperature, in 105 DEG C, then drip and add group part A, group part B and component C, initiator and chain-transfer agent mixed solution, drip, be incubated 1 hour in 2��4 hours;
(2) then add the initiator solution being dissolved in solubility promoter to system, it is incubated 2��4 hours;
(3) adding neutralizing agent to degree of neutralization is 50%��60%, namely obtains water-dispersed acrylic ester resin;
(4) above-mentioned water-dispersed acrylic ester resin is mixed with aziridine crosslinker, coatings additive(s) and deionized water, namely make the acrylate double-component aqueous car paint crosslinked with aziridine.
6. the preparation method of the double-component aqueous car paint of acrylate resin that a kind of aziridine according to claim 5 is crosslinked, it is characterised in that described dosage of crosslinking agent is that crosslinked group contained by acrylate resin and carboxyl and hydroxyl equimolar amount add.
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| CN104788721B (en) * | 2015-04-04 | 2017-12-12 | 河南理工大学 | A kind of composition containing aziridine crosslinker and preparation method thereof |
| CN106947350A (en) * | 2017-02-08 | 2017-07-14 | 佛山沛涂科技有限公司 | A kind of water-based automobile paint containing composite curing system |
| US10920096B2 (en) * | 2018-03-28 | 2021-02-16 | Riso Kagaku Corporation | Oil-based inkjet ink and method for producing oil-based inkjet ink |
| CN109504204A (en) * | 2018-11-06 | 2019-03-22 | 青岛展辰新材料有限公司 | A kind of wooden ware sealing priming paint and preparation method thereof for preventing from seeping on tannic acid |
| CN110752093A (en) * | 2019-10-10 | 2020-02-04 | 深圳市峰泳科技有限公司 | Double-sided-etchable flexible thin-film capacitor material with high dielectric constant and preparation method thereof |
| CN112266755A (en) * | 2020-09-29 | 2021-01-26 | 乐凯胶片股份有限公司 | Water-based paint, adhesive coating, solar cell back sheet and solar cell |
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