CN104610868A - Amino stoving varnish composition with scratch self-remediation function and preparation method of amino stoving varnish composition - Google Patents
Amino stoving varnish composition with scratch self-remediation function and preparation method of amino stoving varnish composition Download PDFInfo
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Abstract
The invention discloses an amino stoving varnish composition with a scratch self-remediation function. The amino stoving varnish composition comprises a hyperbranched polymer, blocked isocyanate resin and amino resin. When a paint film formed after the amino stoving varnish composition with the scratch self-remediation function is coated is radiated in sunshine, the surface temperature of the paint film rises, scratch can be vanished, and thus the scratch self-remediation function is achieved. As polyurethane bonds are stable and elastically reversible, the scratch self-remediation function of the amino stoving varnish composition with a self-cleaning function is good in long-term action. The amino stoving varnish composition is simple in preparation process and applicable to industrial production.
Description
Technical field
The present invention relates to coating and preparation method thereof technical field.More specifically, a kind of amino-stoving varnish composition and method of making the same with cut self-repair function is related to.
Background technology
Amino-stoving varnish with the acrylic resin of hydroxyl or Synolac, aminoresin for main film forming substance, pack with single-component under normal temperature, at relatively high temperatures (about 140 DEG C), chemical reaction is there is between component, form the three dimensional structure with three-dimensional network, there is very high hardness, the excellent performance such as sticking power, high gloss, good guarantor's light tint retention, be widely used in the application of automobile, boats and ships and metal door and window etc.
But existingly can in use still have many defects by quick-setting amino-stoving varnish.Such as, automobile in routine use process, along with wipe car, carwash number of times increase, coating surface inevitably increases a lot of cut, the cut that these cuts produce in coating surface extruding based on hard fine dust, gloss of film can be caused to reduce, and vehicle appearance is affected.Especially black vehicle body, under solar radiation, cut is obvious especially.
Therefore, provide a kind of there is amino-stoving varnish of long-lasting cut self-repair function and preparation method thereof to seem particularly necessary.
Summary of the invention
Technical problem solved by the invention is to provide a kind of amino-stoving varnish composition with cut self-repair function, this product utilizes terminal hydroxy group functional groups numerous in nano level hyper-branched polyester polyol resin and blocked isocyanate to react, produce the polyether polyols with reduced unsaturation network of high crosslink density, a kind of amino-stoving varnish with long-lasting cut self-repair function of preparation.
Second technical problem to be solved by this invention is to provide a kind of preparation method with the amino-stoving varnish composition of cut self-repair function, and the method preparation technology is simple, and suitability for industrialized is produced.
For solving above-mentioned first technical problem, the present invention adopts following technical proposals:
Have an amino-stoving varnish composition for cut self-repair function, said composition comprises: hyperbranched polymer, isocyanate resin and aminoresin.
Preferably, described composition comprises 8wt%-12wt% hyperbranched polymer, the aminoresin of 25wt%-35wt% isocyanic ester and 5wt%-15wt%.
Preferably, described hyperbranched polymer is hyper-branched polyester polyol resin or hyperbranched masked isocyanate resin.
Preferably, described hyperbranched polymer hydroxy radical content counts 6.0wt%-9.0wt% by solid resin, viscosity is 100-1100cPs (25 DEG C); Preferably, the hydroxy radical content of described hyperbranched polymer counts 2.0wt%-5.0wt% by solid resin.
The distinctive dendritic structure of hyperbranched poly ester polyol makes it have nodeless mesh and non-twined; It has numerous terminal hydroxy group functional groups, can form highdensity urethane bonds with isocyanate reaction, and this is the key factor that coating has cut selfreparing.Above 2 is not available for conventional polyester polyvalent alcohol, and common can not substitute hyperbranched poly ester polyol, otherwise cut self-reparing capability disappears.Such as, described hyperbranched polymer is selected from the hyper-branched polyester polyol resin such as BBHA D5025 (CyGLAZ BB 500), CyGLAZ BB 900 (being abbreviated as BB900), BB D5025 of Singapore Science and Technology Ltd. and Nippon Paint (China) Co., Ltd. immediately, and the hyperbranched masked isocyanate resin such as BB 900HDI-35-10%, BB 900HDI-35-30%.
Aminoresin: CYMEL 211 is purchased from CYTEC company, or Luwipal 072 available from BASF; Aminoresin can with part polyol reaction, the effect of aminoresin increases hardness of paint film.
Preferably, the 5%-50wt% that the deblocking temperature of described hyperbranched masked isocyanate resin is 110-150 DEG C, blocked isocyanate functional's content in hyperbranched masked isocyanate resin accounts for the total functional group content of hyperbranched masked isocyanate resin, preferably, described blocked isocyanate functional's content accounts for the 10%-30wt% of the total functional group content of hyperbranched masked isocyanate resin.
Preferably, the deblocking temperature of described blocked isocyanate resin is 110-150 DEG C, isocyanate functional group's content of end-blocking is 8%-12wt% in blocked isocyanate resin
Blocked isocyanate resin is the BL 3175SN (being abbreviated as BL3175) purchased from BAYER company, in blocked isocyanate resin, isocyanate functional group's content of end-blocking is 11.1wt%, deblocking temperature is 130 ~ 140 DEG C, or BL 4265SN, in blocked isocyanate resin, isocyanate functional group's content of end-blocking is 8.1wt%, and deblocking temperature is 130 ~ 140 DEG C; Or purchased from the BLR 8086 of moral modest (Shanghai) Chemical Co., Ltd., in blocked isocyanate resin, isocyanate functional group's content of end-blocking is 11.3wt%, and deblocking temperature is 130 ~ 140 DEG C.
Preferably, described composition also comprises 15.0wt%-25.0wt% Hydroxylated acrylic resin, 1.0wt%-5.0wt% hydroxy polyester resin, 2.0wt%-3.0wt% coatings additive(s), 20.0wt%-30.0wt% thinner.
Preferably, the hydroxy radical content of described Hydroxylated acrylic resin counts 2.5wt%-4.5wt% by pure solid part.
Hydroxylated acrylic resin is purchased from the URACRON CY 430E-70 of DSM N. V., and hydroxy radical content counts 3.0% by pure solid part; Or purchased from the DESMOPHEN A870BA of BAYER company, hydroxy radical content counts 4.3% by pure solid part.
Preferably, the hydroxy radical content of described hydroxy polyester resin counts 4.0%-6.0% by pure solid part.
Containing a certain amount of conventional polyester polyvalent alcohol in formula is consider, mainly in order to improve shock resistance and water tolerance for improving the indivedual physicochemical property of paint film.Hydroxy polyester resin is purchased from Nuplex company SETAL1715VX-74, and hydroxy radical content counts 4.4% by pure solid part, and SETAL 166SS-80, and hydroxy radical content counts 5.8% by pure solid part.
Applicant finds, under the prerequisite that aminoresin exists, uses the hyper-branched polyester polyol resin containing numerous terminal hydroxy group, itself and blocked isocyanate is reacted, makes coating in film-forming process, form the polyether polyols with reduced unsaturation network of high crosslink density.And the urethane bonds that conventional polyester polyvalent alcohol and polyurethane reaction are formed, owing to itself being that linear structure, hydroxyl equivalent are large, the urethane bonds density of formation is little, is not enough to the cut self-repair function supporting paint film.When paint film is subject to hard fine dust extruding, in the highdensity urethane bonds using the hyperbranched poly ester polyol containing distinctive dendritic structure and numerous terminal hydroxy group and blocked isocyanate to react to be formed, hydrogen bond is separable and absorb external energy (20 ~ 25kj/mol), and find new chelating point, and fixing chemical bond is unaffected, now this polymer network is in the state of fixing tension force; When there being solar radiation, coating surface temperature raises, and the polymer network tightened is loosened, and hydrogen bond returns to original position, and cut disappears.
Preferably, described coatings additive(s) is selected from one or more in UV light absorber, photostabilizer, flow agent, coupling agent, siccative, toughner, adhesion promoter, defoamer, anti-skinning agent, matting agent, mould inhibitor and static inhibitor.
Preferably, described coatings additive(s) comprises the UV light absorber of 0.1-0.8wt%, 0.1-0.5wt% photostabilizer, 0.3-1.0wt% flow agent and 0.3-0.8wt% coupling agent.
Flow agent is BYK-315, BYK-306 (purchased from BYK company) or Worlee add 315 (purchased from Beijing Teng Xinsheng development in science and technology company limited); UV light absorber is TINUVIN-1130, TINUVIN-400 (available from BASF) or CHISORB5228 (purchased from Double Bond Chemical(DBC)Ind. Co., Ltd.); Photostabilizer is TINUVIN-292, TINUVIN-123 (available from BASF) or CHISORB523 (purchased from Double Bond Chemical(DBC)Ind. Co., Ltd.); Coupling agent is DC 6040 (purchased from Dow Corning Corporation) or KBM 403 (purchased from Shin-Etsu Chemial Co., Ltd).
Preferably, described thinner is selected from one or more in esters solvent, ketones solvent, alcoholic solvent and alcohol ether solvent; Preferably, described esters solvent is selected from one or more in ethyl acetate, butylacetate, 1-Methoxy-2-propyl acetate, 3-ethoxyl ethyl propionate and pentyl acetate; Preferably, described ketones solvent is selected from one or more in acetone, butanone, pimelinketone, cyclopentanone and mibk; Preferably, described alcoholic solvent is selected from one or more in methyl alcohol, ethanol and butanols; Preferably, described ether solvent is selected from one or more in glycol-ether, ethylene glycol-ether, Diethylene Glycol-ether.
For solving above-mentioned second technical problem, the present invention adopts following technical proposals, and a kind of preparation method with the amino-stoving varnish composition of cut self-repair function, comprises the following steps:
(1) under agitation, in reactor, add the hyperbranched resin of 10.0wt%-20.0wt% thinner and formula ratio successively, continue to stir 8-15min;
(2) in reactor, add 5.0wt%-15.0wt% aminoresin, 15.0wt%-25.0wt% Hydroxylated acrylic resin, 25.0wt%-35.0wt% blocked isocyanate resin, 1.0wt%-5.0wt% hydroxy polyester resin and 2.0wt%-3.0wt% coatings additive(s) successively, filter after stirring 20-40min and obtain the amino-stoving varnish with cut self-repair function.
Preferably, in step (1), described stirring velocity is: 200-250r/min; In step (2), described stirring velocity is: 300-350r/min.
Add thinner under agitation and hyperbranched poly ester polyol object is that hyper-branched polyester polyol resin is uniformly dispersed in a solvent, avoid because its numerous terminal hydroxy group functional group makes intermolecular reunion itself, follow-up stirring can not make it dispersion, affect the cross-linking density of urethane bonds, thus reduce cut self-repair function.
Beneficial effect of the present invention is as follows:
(1) the amino-stoving varnish composition with cut self-repair function provided of the present invention, after application, gained paint film is when solar radiation, and coating surface temperature raises, and cut disappears, and has cut self-repair function.
(2) because urethane bonds is stable, elasticity is reversible, the cut self-repair function of the amino-stoving varnish of self-cleaning function of the present invention is made to have long-lasting.
(3) preparation technology of the present invention is simple, and suitability for industrialized is produced.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 illustrates: the structural representation of CyGLAZ hyperbranched polymer;
Fig. 2 illustrates: the structural representation of common non-hyperbranched polymer;
Fig. 3 illustrates: cut self-repair procedure schematic diagram;
Fig. 4 illustrates: the picture before cut selfreparing amino-stoving varnish scratch removal prepared by embodiment 2;
Fig. 5 illustrates: the picture after cut selfreparing amino-stoving varnish scratch removal prepared by embodiment 2;
Fig. 6 illustrates: the picture before cut selfreparing amino-stoving varnish scratch removal prepared by embodiment 9;
Fig. 7 illustrates: the picture after cut selfreparing amino-stoving varnish scratch removal prepared by embodiment 9.
Embodiment
In order to be illustrated more clearly in the present invention, below in conjunction with preferred embodiments and drawings, the present invention is described further.Parts similar in accompanying drawing represent with identical Reference numeral.It will be appreciated by those skilled in the art that specifically described content is illustrative and nonrestrictive, should not limit the scope of the invention with this below.
Hyperbranched polymer is purchased from the Singapore BBHA D5025 (CyGLAZ BB 500) of Science and Technology Ltd. and Nippon Paint (China) Co., Ltd., CyGLAZ BB 900, BB D5025 immediately, or BB 900HDI-35-10%, BB 900HDI-35-30%;
BB900-HDI-35-10% (hyperbranched resin BB900 10% hydroxyl by HDI-3,5-dimethyl pyrazole replace) synthesis:
The synthesis of the semiclosed prepolymer of HDI-3,5-dimethyl pyrazole
Add the HDI of 1mol, solvent acetic acid butyl ester, catalyst dibutyltin dilaurylate to reactor, be warming up to 70 DEG C, drip 1mol 3 in 70 DEG C ± 5 DEG C, 5-dimethyl pyrazole, drips and terminates insulation, react about 1 hour, survey NCO equivalent to 288 ~ 308g/eq, then cool termination.
The synthesis of BB900-HDI-35-10%
By the above-mentioned HDI-3 of BB900 and 0.1mol containing 1 hydroxy group, the semiclosed prepolymer of 5-dimethyl pyrazole adds reactor, catalyst dibutyltin dilaurylate is added under stirring, be warming up to 80 DEG C, in 80 DEG C of insulations sampling after 1 hour, detect NCO%, until NCO%<0.1% is qualified, about 2 hours of reaction times.Qualified rear cooling, adds diluting solvent butylacetate, filters discharging after stirring.Obtain the polymkeric substance of Mn about 3800, Mw about 14600.
BB900-HDI-35-30% (hyperbranched resin BB900 30% hydroxyl by HDI-3,5-dimethyl pyrazole replace) synthesis:
By the above-mentioned HDI-3 of BB900 and 0.3mol containing 1 hydroxy group, the semiclosed prepolymer of 5 dimethyl pyrazole adds reactor, catalyst dibutyltin dilaurylate is added under stirring, be warming up to 80 DEG C, in 80 DEG C of insulations sampling after 1 hour, detect NCO%, until NCO%<0.1% is qualified, about 2 hours of reaction times.Qualified rear cooling, adds diluting solvent butylacetate, filters discharging after stirring.Obtain the polymkeric substance of Mn about 3800, Mw about 24100.
Hydroxylated acrylic resin is the URACRON CY 430E-70 purchased from DSM N. V.; Or be the DESMOPHEN A870BA purchased from BAYER company;
Blocked isocyanate resin is BL 3175SN purchased from BAYER company or BL 4265SN; Or be the BLR 8086 purchased from moral modest (Shanghai) Chemical Co., Ltd.;
Aminoresin is US-138BB70 or US-146BB72 purchased from Nuplex company; Or be the Luwipal 072 of available from BASF;
Hydroxy polyester resin is purchased from Nuplex company SETAL 1715VX-74 and SETAL 166SS-80;
Flow agent is BYK-315, BYK-306 or Worlee add 315;
UV light absorber is TINUVIN-1130, TINUVIN-400 or CHISOKB5228;
Photostabilizer is TINUVIN-292, TINUVIN-123 or CHISOKB523;
Coupling agent is DC 6040 or KBM 403.
Embodiment 1
Table 1 embodiment 1 raw material weight percentage ratio
By the butylacetate of 9wt%, the 1-Methoxy-2-propyl acetate of 9wt% and the propyl carbinol of 2.1wt% add in stirring tank, the CyGLAZ BB 900 of 10.3wt% is slowly added under 200r/min mixing speed, in BB900, solid resin hydroxy radical content is 8.45%, the US-138BB-70 of 8.5wt% is slowly added successively after stirring 10min, the URACRON CY 430E-70 of 23.9wt%, the BL 3175 of 27.2wt%, the SETAL 1715VX-74 of 3.4wt%, the BYK-315 of 0.3wt%, the TINUVIN-400 of 0.6wt%, the KBM-403 of TINUVIN-292 and 0.8wt% of 0.3wt%, rise stir speed (S.S.) after feeding intake to filter after 380r/min continues to stir 30min, discharging obtains the amino-stoving varnish with cut self-repair function.
The performance test with the amino-stoving varnish of cut self-repair function prepared by embodiment 1
The obtained amino-stoving varnish viscosity with cut self-repair function is diluted to 24 ~ 26 seconds and (is coated with-4 flow cups, 25 DEG C), wet and touch wet spray on black colored paint, (rock field 101 type spray gun, spray pressure 0.4MPa control dried film thickness 25 ~ 30 μm), levelling 6 ~ 8min, last at 140 DEG C, baking 30min, namely obtains the amino-stoving varnish coating of cut self-repair function.
The detection method of performance is in table 2:
Table 2 method for testing performance
Comparative example 1 is the hyperbranched resin of the medium amount of hydroxyl groups of Hydroxylated acrylic resin alternate embodiment 1 by the amount of hydroxyl groups such as commercially available, and unclassified stores consumption is constant.
Comparative example 2 is blocked isocyanate resin in the mass substitution embodiments 1 such as commercially available aminoresin, and unclassified stores consumption is constant.
Comparative example 3 is aminoresin in the mass substitution embodiments 1 such as commercially available blocked isocyanate resin, and unclassified stores consumption is constant.
The baking vanish performance of embodiment 1 and comparative example 1,2 is in table 3.
The performance of the baking vanish of table 3 embodiment 1 and comparative example
As can be seen from Table 3, amino-stoving varnish excellent performance prepared by embodiment 1, its paint film has cut self-repair function.And hyperbranched resin in the Hydroxylated acrylic resin alternate embodiment 1 of the amount of hydroxyl groups such as comparative example 1 use, thus the urethane bonds of high crosslink density cannot be formed, therefore comparative example 1 paint film does not possess cut self-repair function.Fig. 1, Fig. 2 illustrate the structural representation of CyGLAZ hyperbranched resin and conventional polyester polyvalent alcohol, can find out thus, hyperbranched resin has distinctive dendritic structure and numerous terminal hydroxy group, make it with blocked isocyanate reaction after can form highdensity urethane bonds; Conventional polyester polyvalent alcohol also can form urethane bonds with polyurethane reaction, but to be linear structure, hydroxyl equivalent large for itself, and the urethane bonds density of formation is little, is not enough to the cut self-repair function supporting paint film.Fig. 3 illustrates the schematic diagram of cut self-repair procedure.In comparative example 3, aminoresin and part polyol reaction, increase hardness of paint film, the paint film therefore without aminoresin has cut self-repair function, but paint film feels like jelly, loss of gloss.
Water-fast and weatherometer is simulated: model prepared by embodiment 1 and comparative example 1,2 is placed in tank and weatherometer respectively, is taken out after the specified time, then surveys cut self-repairability, the results are shown in Table 4.
Table 4 is water-fast and the performance of the baking vanish of embodiment 1 and comparative example after anti-aging test
Embodiment 2
Repeat embodiment 1, its difference is only, embodiment 2 raw material weight percentage ratio is as table 5.The hydroxy radical content of wherein said hyper-branched polyester polyol resin counts 8.6% by solid resin, viscosity is 185cPs, 25 DEG C; The blocked isocyanate content of described blocked isocyanate resin is 8.1%, deblocking temperature is 130 DEG C.
Table 5 embodiment 2 raw material weight percentage ratio
(1) formula ratio thinner is added in the reactor of band stirring, under whipped state, then slowly add hyper-branched polyester polyol resin continue to stir 10min; Stirring velocity is 200r/min;
(2) in the reactor of step (1), add formula ratio aminoresin, Hydroxylated acrylic resin, blocked isocyanate resin, hydroxy polyester resin and coatings additive(s) successively, continuing low whipping speed is: filter the amino-stoving varnish obtaining having cut self-repair function after stirring 30min under the condition of 380r/min.Fig. 4 illustrates picture before cut selfreparing baking vanish scratch removal; Fig. 5 illustrates picture after cut selfreparing baking vanish scratch removal, and as shown in Figure 4, Figure 5, the obtained paint film of products therefrom has good cut self-repair function.
Embodiment 3
Embodiment 3 raw material weight percentage ratio is as table 6, and the hydroxy radical content of wherein said hyper-branched polyester polyol resin counts 6.7% by solid resin, viscosity is 130cPs, 25 DEG C; The blocked isocyanate content of described blocked isocyanate resin is 11.1%, deblocking temperature is 125 DEG C.
Table 6 embodiment 3 raw material weight percentage ratio
(1) formula ratio thinner is added in the reactor of band stirring, under whipped state, then slowly add hyper-branched polyester polyol resin continue to stir 10min; Stirring velocity is 250r/min;
(2) in the reactor of step (1), add the aminoresin of formula ratio, Hydroxylated acrylic resin, blocked isocyanate resin, hydroxy polyester resin and coatings additive(s) successively, continuing low whipping speed is: filter the amino-stoving varnish obtaining having cut self-repair function after stirring 30min under the condition of 360r/min.
Embodiment 4
Embodiment 4 raw material weight percentage ratio is as table 7, and wherein said hyperbranched masked isocyanate resin counts 2.7% by the hydroxy radical content of solid resin, blocked isocyanate functional's content in hyperbranched masked isocyanate resin is 1.9wt%; The deblocking temperature of blocked isocyanate resin is 130 ~ 140 DEG C, in blocked isocyanate resin isocyanate functional group's content of end-blocking be 11.3wt%,
Table 7 embodiment 4 raw material weight number
(1) formula ratio thinner is added in the reactor of band stirring, under whipped state, then slowly add the hyperbranched masked isocyanate resin of formula ratio continue to stir 10min; Stirring velocity is 250r/min;
(2) in the reactor of step (1), formula ratio aminoresin, Hydroxylated acrylic resin, blocked isocyanate resin, hydroxy polyester resin and coatings additive(s) is added successively, low whipping speed is after stirring 30min under the condition of 350r/min, filters and obtains the amino-stoving varnish with cut self-repair function.
Embodiment 5,6
With embodiment 1, its difference is only, the hydroxy radical content of described hyperbranched resin is respectively by solid resin: 6.7%, 8.6%.
Embodiment 7,8
With embodiment 1, its difference is only, in described blocked isocyanate resin, isocyanate functional group's content of end-blocking is respectively 8.1wt%, 11.1wt% by pure solid part.
The cut selfreparing measure of merit of the amino-stoving varnish coating of embodiment 2-8 the results are shown in Table 8.The amino-stoving varnish coating cut self-repairability of embodiment 2-8 does not weaken along with the impact of the factor such as aging, water-fast completely, has cut selfreparing long-lasting.
The cut self-reparing capability of the amino-stoving varnish coating of table 8 embodiment 2-8
| Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| Scratch removal | Can repair | Can repair | Can repair | Can repair | Can repair | Can repair | Can repair |
Embodiment 9
With embodiment 3, its difference is only, the order of addition(of ingredients) of step (1), (2) adds thinner, Hydroxylated acrylic resin, hyper-branched polyester polyol resin, aminoresin, blocked isocyanate resin, hydroxy polyester resin and coatings additive(s) successively, stirring velocity is stir under the condition of 300r/min, continue after feeding intake to stir 30min, discharging obtains product.Made paint film cut self-repair function reduces, and namely all cuts can not be repaired completely.
Fig. 6 illustrates: picture before scratch removal; Fig. 7 illustrates: picture after scratch removal.As shown in Figure 6, Figure 7, after changing order of addition(of ingredients), the paint film cut self-repair function reduction that products therefrom is obtained.
Embodiment 10
With embodiment 4, its difference is only, the order of addition(of ingredients) of step (1), (2) adds thinner, aminoresin, Hydroxylated acrylic resin, hyperbranched masked isocyanate resin, blocked isocyanate resin, hydroxy polyester resin and coatings additive(s) successively, stirring velocity is stir under 300r/min condition, continue after feeding intake to stir 30min, discharging obtains product.Made paint film cut self-repair function reduces, and namely all cuts can not be repaired completely.
Major cause is that hyperbranched resin is not uniformly dispersed first in a solvent, its numerous terminal hydroxy group functional group can cause intermolecular reunion itself, follow-up stirring can not make it dispersion, finally has influence on the cross-linking density of urethane bonds, thus reduces cut self-repair function.
Embodiment 11
With embodiment 1, its difference is only, blocked isocyanate resin becomes BLR8086 from BL 3175, and embodiment 11 is raw materials used in table 9.
Table 9 embodiment 11 raw material weight number
Amino-stoving varnish coating test result and the embodiment 1 of embodiment 11 preparation are close.
Obviously; the above embodiment of the present invention is only for example of the present invention is clearly described; and be not the restriction to embodiments of the present invention; for those of ordinary skill in the field; can also make other changes in different forms on the basis of the above description; here cannot give exhaustive to all embodiments, every belong to technical scheme of the present invention the apparent change of extending out or variation be still in the row of protection scope of the present invention.
Claims (14)
1. there is an amino-stoving varnish composition for cut self-repair function, it is characterized in that, said composition
Comprise: hyperbranched polymer, blocked isocyanate resin and aminoresin.
2. amino-stoving varnish composition according to claim 1, is characterized in that: described composition comprises 8wt%-12wt% hyperbranched polymer, the aminoresin of 25wt%-35wt% blocked isocyanate resin and 5wt%-15wt%.
3. amino-stoving varnish composition according to claim 1 and 2, is characterized in that, described hyperbranched polymer is hyper-branched polyester polyol resin or hyperbranched masked isocyanate resin.
4. a kind of amino-stoving varnish composition with cut self-repair function according to claim 3, it is characterized in that, the hydroxy radical content of described hyper-branched polyester polyol resin counts 6.0wt%-9.0wt% by solid resin, the viscosity of 25 DEG C is 100-1100cPs.
5. a kind of amino-stoving varnish composition with cut self-repair function according to claim 3, it is characterized in that, the deblocking temperature of described hyperbranched masked isocyanate resin is 110-150 DEG C, 5%-50wt% that blocked isocyanate functional's content in hyperbranched masked isocyanate resin accounts for the total functional group content of hyperbranched masked isocyanate resin; Preferably, described blocked isocyanate functional's content accounts for the 10%-30wt% of the total functional group content of hyperbranched masked isocyanate resin.
6. a kind of amino-stoving varnish composition with cut self-repair function according to claim 1, it is characterized in that, the deblocking temperature of described blocked isocyanate resin is 110-150 DEG C, isocyanate functional group's content of end-blocking is 8%-12wt% in blocked isocyanate resin.
7. a kind of amino-stoving varnish composition with cut self-repair function according to claim 1, it is characterized in that, described composition also comprises 15.0wt%-25.0wt% Hydroxylated acrylic resin, 1.0wt%-5.0wt% hydroxy polyester resin, 2.0wt%-3.0wt% coatings additive(s), 20.0wt%-30.0wt% thinner.
8. a kind of amino-stoving varnish composition with cut self-repair function according to claim 7, is characterized in that, the hydroxy radical content of described Hydroxylated acrylic resin counts 2.5wt%-4.5wt% by pure solid part.
9. a kind of amino-stoving varnish composition with cut self-repair function according to claim 7, is characterized in that, the hydroxy radical content of described hydroxy polyester resin counts 4.0%-6.0% by pure solid part.
10. a kind of amino-stoving varnish composition with cut self-repair function according to claim 7, it is characterized in that, described coatings additive(s) is selected from one or more in UV light absorber, photostabilizer, flow agent, coupling agent, siccative, toughner, adhesion promoter, defoamer, anti-skinning agent, matting agent, mould inhibitor and static inhibitor.
11. a kind of amino-stoving varnish compositions with cut self-repair function according to claim 10, it is characterized in that, described coatings additive(s) comprises the UV light absorber of 0.1-0.8wt%, 0.1-0.5wt% photostabilizer, 0.3-1.0wt% flow agent and 0.3-0.8wt% coupling agent.
12. a kind of amino-stoving varnish compositions with cut self-repair function according to claim 7, it is characterized in that, described thinner is selected from one or more in esters solvent, ketones solvent, alcoholic solvent and alcohol ether solvent; Preferably, described esters solvent is selected from one or more in ethyl acetate, butylacetate, 1-Methoxy-2-propyl acetate, 3-ethoxyl ethyl propionate and pentyl acetate; Preferably, described ketones solvent is selected from one or more in acetone, butanone, pimelinketone, cyclopentanone and mibk; Preferably, described alcoholic solvent is selected from one or more in methyl alcohol, ethanol and butanols; Preferably, described ether solvent is selected from one or more in glycol-ether, ethylene glycol-ether, Diethylene Glycol-ether.
13. 1 kinds of preparation methods with the amino-stoving varnish composition of cut self-repair function, is characterized in that, comprise the following steps:
(1) under agitation, in reactor, add the hyperbranched polymer of 10.0wt%-20.0wt% thinner and tested number successively, continue to stir 8-15min;
(2) in reactor, add 5.0wt%-15.0wt% aminoresin, 15.0wt%-25.0wt% Hydroxylated acrylic resin, 25.0wt%-35.0wt% isocyanate resin, 1.0wt%-5.0wt% hydroxy polyester resin and 2.0wt%-3.0wt% coatings additive(s) successively, filter after stirring 20-40min and obtain the amino-stoving varnish with cut self-repair function.
14. preparation methods according to claim 13, is characterized in that: in step (1), described stirring velocity is: 200-250r/min; In step (2), described stirring velocity is: 300-350r/min.
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| CN104962152A (en) * | 2015-07-14 | 2015-10-07 | 扬州市祥华新材料科技有限公司 | Alumite chromatographic dye containing hyperbranched polymer and preparation method of alumite chromatographic dye |
| CN105384892A (en) * | 2015-12-24 | 2016-03-09 | 上海金力泰化工股份有限公司 | Synthesis method for accelerant used for curing amino stoving varnish at low temperature |
| CN105505067A (en) * | 2016-01-28 | 2016-04-20 | 廊坊立邦涂料有限公司 | Anti-indentation amino baking paint and preparation method thereof |
| CN105860722A (en) * | 2016-04-21 | 2016-08-17 | 廊坊立邦涂料有限公司 | Single-component, high-solid-content and low-volatility organic compound and environment-friendly type varnish composition and preparation method and application of varnish composition |
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| CN108084861A (en) * | 2017-12-29 | 2018-05-29 | 常州山由帝杉防护材料制造有限公司 | Selfreparing oil-stain-preventing coating and preparation method thereof, protecting film comprising the coating and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353396A (en) * | 2008-09-08 | 2009-01-28 | 江苏柏鹤涂料有限公司 | Heat-setting resin based on unsaturated polyester resins and mirror back metal plating protecting coating thereof |
| CN101914201A (en) * | 2010-07-08 | 2010-12-15 | 广东雅图化工有限公司 | Method for synthesizing star-like super-branched polymer resin and water-based finish varnish for vehicles |
| CN102257085A (en) * | 2008-12-17 | 2011-11-23 | 巴斯夫欧洲公司 | Quick-drying coating compounds |
-
2015
- 2015-01-09 CN CN201510012072.2A patent/CN104610868B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353396A (en) * | 2008-09-08 | 2009-01-28 | 江苏柏鹤涂料有限公司 | Heat-setting resin based on unsaturated polyester resins and mirror back metal plating protecting coating thereof |
| CN102257085A (en) * | 2008-12-17 | 2011-11-23 | 巴斯夫欧洲公司 | Quick-drying coating compounds |
| CN101914201A (en) * | 2010-07-08 | 2010-12-15 | 广东雅图化工有限公司 | Method for synthesizing star-like super-branched polymer resin and water-based finish varnish for vehicles |
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| CN104962152B (en) * | 2015-07-14 | 2017-04-19 | 扬州市祥华新材料科技有限公司 | Alumite chromatographic dye containing hyperbranched polymer and preparation method of alumite chromatographic dye |
| CN104962152A (en) * | 2015-07-14 | 2015-10-07 | 扬州市祥华新材料科技有限公司 | Alumite chromatographic dye containing hyperbranched polymer and preparation method of alumite chromatographic dye |
| CN105384892A (en) * | 2015-12-24 | 2016-03-09 | 上海金力泰化工股份有限公司 | Synthesis method for accelerant used for curing amino stoving varnish at low temperature |
| CN105505067A (en) * | 2016-01-28 | 2016-04-20 | 廊坊立邦涂料有限公司 | Anti-indentation amino baking paint and preparation method thereof |
| CN105860722B (en) * | 2016-04-21 | 2019-06-28 | 廊坊立邦涂料有限公司 | A kind of one pack system, large arch dam, low VOC, environmentally friendly clear coat composition, preparation method and its usage |
| CN105860722A (en) * | 2016-04-21 | 2016-08-17 | 廊坊立邦涂料有限公司 | Single-component, high-solid-content and low-volatility organic compound and environment-friendly type varnish composition and preparation method and application of varnish composition |
| CN106634156A (en) * | 2016-12-28 | 2017-05-10 | 上海金力泰化工股份有限公司 | High-weatherability ultraviolet absorbent, automobile paint containing same and preparation methods thereof |
| CN107057547A (en) * | 2017-05-15 | 2017-08-18 | 立邦涂料（中国）有限公司 | A kind of acroleic acid polyurethane type coating varnish composition, preparation method and its usage |
| CN107312435A (en) * | 2017-07-13 | 2017-11-03 | 洛阳双瑞防腐工程技术有限公司 | A kind of super water-fast self-repair type Aqueous acrylic urethane coating and preparation method thereof |
| CN108084861A (en) * | 2017-12-29 | 2018-05-29 | 常州山由帝杉防护材料制造有限公司 | Selfreparing oil-stain-preventing coating and preparation method thereof, protecting film comprising the coating and preparation method thereof |
| CN108084861B (en) * | 2017-12-29 | 2023-08-04 | 常州山由帝杉防护材料制造有限公司 | Self-repairing oil stain-proof coating and preparation method thereof, protective film containing coating and preparation method thereof |
| CN108715728A (en) * | 2018-05-31 | 2018-10-30 | 惠州大东涂料有限责任公司 | A kind of high abrasion can repair scratch polyurethane coating automatically |
| CN111269389A (en) * | 2018-12-05 | 2020-06-12 | 中国石油化工股份有限公司 | Reversible crosslinking aliphatic polyester and preparation method thereof |
| CN110804354A (en) * | 2019-11-15 | 2020-02-18 | 广州立邦涂料有限公司 | Scratch-resistant matte varnish composition for automobile hub, scratch-resistant matte varnish containing scratch-resistant matte varnish composition for automobile hub, preparation and application |
| CN110804376A (en) * | 2019-11-21 | 2020-02-18 | 廊坊立邦涂料有限公司 | Composition of high-temperature corrosion-resistant transparent primer for automobile hub and preparation method of composition |
| CN110804376B (en) * | 2019-11-21 | 2022-02-08 | 廊坊立邦涂料有限公司 | Composition of high-temperature corrosion-resistant transparent primer for automobile hub and preparation method of composition |
| CN110964393A (en) * | 2019-12-05 | 2020-04-07 | 廊坊立邦涂料有限公司 | Varnish composition with anti-indentation self-repairing function of protective film and preparation method and application thereof |
| CN114686067A (en) * | 2020-12-31 | 2022-07-01 | 立邦涂料（中国）有限公司 | Varnish paint composition and application thereof |
| CN114686067B (en) * | 2020-12-31 | 2024-08-13 | 立邦涂料（中国）有限公司 | Varnish coating composition and application thereof |
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