A kind of wear-resisting, scratch resistant coatings and preparation method thereof
Technical field
The present invention relates to a kind of wear-resisting, scratch resistant coatings and preparation method thereof.
Background technology
After surface of plastic products is covered with paint, lacquer, colour wash, etc., the wearability and scratch resistance of coating are two important indicators.Wearability and scratch resistance
Hardness and toughness of the wiping property all with material are relevant, but wearability is the journey that material is peeled off from parent under identical stress condition
Degree, its reflection is surface property of the material under small stress long duration of action, and scratch resistance reflection is then material big
Surface nature under the effect of stress short time.Conventional wear-resistant paint is usually silicone-based coating at present, the coating that the coating is obtained
Scratch resistance is still to be improved.The method for improving coating scraping and wiping resistance performance is typically to add scratch resistance liniment in coating, for example
Amide-type, wax class lubricant, but add lubricant during above-mentioned scratch resistance liniment has use and separate out so as to cause coating to be sent out
Viscous problem is produced.
The content of the invention
In order to solve the above-mentioned technical problem, the invention provides a kind of wear-resisting, scratch resistant coatings and preparation method thereof so that
Coating has excellent wearability and scratch resistance, and causes the problem of sticky finiss in the absence of lubricant precipitation.
Claimed one kind is wear-resisting, scratch resistant coatings, and it is prepared via a method which to obtain:
(1) 30-50 weight portions alkaline silica sol, 0-10 weight portions distilled water and 2-6 weight portion second are added in the reactor
The mixed liquor of acid, intensification starts that the alcoxyl of the degree of functionality of 50-60 weight portions at least two is added dropwise when the temperature of system is reached 60 DEG C
Base silane, 1-3 hours completion of dropping, during dropwise addition control reaction system temperature between 60 DEG C -72 DEG C, completion of dropping
Temperature rising reflux 0.5-2 hours afterwards, cool and obtain reaction solution;
(2) 0.01-0.03 part by weight of carbon black is added in 15-20 weight portion silane couplers, ultrasonic disperse 2-3 hours
Obtain mixed liquor;
(3) 6-8 weight portion polytetrafluoroethylene (PTFE) temperature rising reflux, system backflow 5-6 are added in the reaction solution that step (1) is obtained
Lower the temperature after hour, mixed liquor and 0-16 parts by weight solvent that step (2) is obtained, stirring are added when the temperature of system is less than 40 DEG C
Coating is obtained after 1-2 hours.
The alkaline silica sol particle diameter is 10-15nm, and the alkaline silica sol is water silica sol.
The alkoxy silane of at least two degree of functionality be selected from MTMS, MTES,
In dimethyldimethoxysil,ne, dimethyldiethoxysilane, phenyl triethoxysilane, phenyltrimethoxysila,e extremely
Few one kind.
The solvent is selected from ethanol, normal propyl alcohol, isopropanol, butanol, isobutanol, butyl glycol ether, propylene glycol monomethyl ether, dipropyl
At least one in keto-alcohol, ethylene glycol ether acetate.
The silane coupler is γ-(oxygen of 2,3- epoxies third) propyl trimethoxy silicane, γ-(oxygen of 2,3- epoxies third) third
Ethyl triethoxy silicane alkane, γ-mercaptopropyl trimethoxysilane, gamma-mercaptopropyltriethoxysilane, γ-mercapto hydroxypropyl methyl diformazan
At least one in TMOS, γ-mercapto hydroxypropyl methyl diethoxy silane.
The application has an advantageous effect in that compared with prior art:
The mixed liquor that the application passes through introducing carbon black and silane coupler in system, and polytetrafluoroethylene (PTFE), carry significantly
The wearability and scratch resistance of coating high, and separated out in the absence of lubricant and cause the problem of sticky finiss.The coating can be extensive
For coating various thermoplastics, such as ABS, polystyrene, lucite.
Specific embodiment
Embodiment 1
A kind of wear-resisting, scratch resistant coatings, it is prepared via a method which to obtain:
(1) mixed liquor of 30g alkaline silica sols and 2.5g acetic acid is added in the reactor, and intensification reaches the temperature of system
Start that 60g MTESs are added dropwise at 60 DEG C, 2 hours completion of dropping control the temperature of reaction system during dropwise addition
It it is 60 DEG C, temperature rising reflux 1 hour, cools and obtain reaction solution after completion of dropping;Wherein, alkaline silica sol particle diameter is
12nm;
(2) 0.02g carbon blacks are added in 15g γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, ultrasonic disperse 2
Hour obtains mixed liquor;
(3) 6g polytetrafluoroethylene (PTFE) temperature rising reflux, system is added to be dropped after flowing back 5 hours in the reaction solution that step (1) is obtained
Temperature, the mixed liquor and 10g isopropanols for adding step (2) to obtain when the temperature of system is less than 40 DEG C, stirring is applied after 2 hours
Material.
Embodiment 2
A kind of wear-resisting, scratch resistant coatings, it is prepared via a method which to obtain:
(1) mixed liquor of 40g alkaline silica sols and 6g acetic acid is added in the reactor, and intensification makes the temperature of system reach 60
DEG C when start to be added dropwise 55g MTMSs, 1 hour completion of dropping, the temperature that reaction system is controlled during dropwise addition is
70 DEG C, temperature rising reflux 2 hours, cool and obtain reaction solution after completion of dropping;Wherein, alkaline silica sol particle diameter is
10nm;
(2) 0.01g carbon blacks are added in 17g gamma-mercaptopropyltriethoxysilanes, ultrasonic disperse is mixed for 3 hours
Liquid;
(3) 8g polytetrafluoroethylene (PTFE) temperature rising reflux, system is added to be dropped after flowing back 5 hours in the reaction solution that step (1) is obtained
Temperature, the mixed liquor and 16g butyl glycol ethers for adding step (2) to obtain when the temperature of system is less than 40 DEG C, stirring is obtained after 2 hours
To coating.
Embodiment 3
A kind of wear-resisting, scratch resistant coatings, it is prepared via a method which to obtain:
(1) mixed liquor of 50g alkaline silica sols and 4g acetic acid is added in the reactor, and intensification makes the temperature of system reach 60
DEG C when start be added dropwise 50g dimethyldimethoxysil,nes, 3 hours completion of dropping, during dropwise addition control reaction system temperature
It it is 65 DEG C, temperature rising reflux 0.5 hour, cools and obtain reaction solution after completion of dropping;Wherein, alkaline silica sol particle diameter is
15nm;
(2) 0.03g carbon blacks are added in 20g γ-(2,3- the third oxygen of epoxy) propyl-triethoxysilicane, ultrasonic disperse 3
Hour obtains mixed liquor;
(3) 8g polytetrafluoroethylene (PTFE) temperature rising reflux, system is added to be dropped after flowing back 6 hours in the reaction solution that step (1) is obtained
Temperature, the mixed liquor for adding step (2) to obtain when the temperature of system is less than 40 DEG C, stirring obtains coating after 1 hour.
Embodiment 4
A kind of wear-resisting, scratch resistant coatings, it is prepared via a method which to obtain:
(1) mixed liquor of 45g alkaline silica sols, 9g distilled water and 2g acetic acid is added in the reactor, and intensification makes system
Temperature starts that 60g phenyl triethoxysilanes are added dropwise when reaching 60 DEG C, and 1 hour completion of dropping controls reactant during dropwise addition
The temperature of system is 68 DEG C, and temperature rising reflux 1 hour, cools and obtain reaction solution after completion of dropping;Wherein, alkaline silica sol particle
A diameter of 10nm;
(2) 0.02g carbon blacks are added in 15g γ-mercapto hydroxypropyl methyl diethoxy silane, ultrasonic disperse is obtained for 2 hours
Mixed liquor;
(3) 7g polytetrafluoroethylene (PTFE) temperature rising reflux, system is added to be dropped after flowing back 5 hours in the reaction solution that step (1) is obtained
Temperature, the mixed liquor for adding step (2) to obtain when the temperature of system is less than 40 DEG C, stirring obtains coating after 2 hours.
Embodiment 5
A kind of wear-resisting, scratch resistant coatings, it is prepared via a method which to obtain:
(1) mixed liquor of 30g alkaline silica sols, 5g distilled water and 5g acetic acid is added in the reactor, and intensification makes system
Temperature starts that 52g MTMSs are added dropwise when reaching 60 DEG C, and 1 hour completion of dropping controls reactant during dropwise addition
The temperature of system is 60 DEG C, and temperature rising reflux 1 hour, cools and obtain reaction solution after completion of dropping;Wherein, alkaline silica sol particle
A diameter of 15nm;
(2) 0.01g carbon blacks are added in 15g γ-(2,3- the third oxygen of epoxy) propyl-triethoxysilicane, ultrasonic disperse 2
Hour obtains mixed liquor;
(3) 8g polytetrafluoroethylene (PTFE) temperature rising reflux, system is added to be dropped after flowing back 5 hours in the reaction solution that step (1) is obtained
Temperature, the mixed liquor and 2g butyl glycol ethers, 8g ethylene glycol ethyl ether vinegar for adding step (2) to obtain when the temperature of system is less than 40 DEG C
Acid esters, stirring obtains coating after 2 hours.
Embodiment 6
A kind of wear-resisting, scratch resistant coatings, it is prepared via a method which to obtain:
(1) mixed liquor of 50g alkaline silica sols, 10g distilled water and 4g acetic acid is added in the reactor, and intensification makes system
Temperature starts that 56g phenyltrimethoxysila,es are added dropwise when reaching 60 DEG C, and 2 hours completion of dropping control reactant during dropwise addition
The temperature of system is 66 DEG C, and temperature rising reflux 0.5 hour, cools and obtain reaction solution after completion of dropping;Wherein, alkaline silica sol
The a diameter of 10nm of grain;
(2) 0.02g carbon blacks are added in 18g γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, ultrasonic disperse 2
Hour obtains mixed liquor;
(3) 6g polytetrafluoroethylene (PTFE) temperature rising reflux, system is added to be dropped after flowing back 5 hours in the reaction solution that step (1) is obtained
Temperature, the mixed liquor and 4g DAAs, 8g isobutanols for adding step (2) to obtain when the temperature of system is less than 40 DEG C, stirring 1 is small
When after obtain coating.
Comparative example 1
The coating is prepared via a method which to obtain:
(1) mixed liquor of 30g alkaline silica sols and 2.5g acetic acid is added in the reactor, and intensification reaches the temperature of system
Start that 60g MTESs are added dropwise at 60 DEG C, 2 hours completion of dropping control the temperature of reaction system during dropwise addition
It it is 60 DEG C, temperature rising reflux 1 hour, cools and obtain reaction solution after completion of dropping;Wherein, alkaline silica sol particle diameter is
12nm;
(2) 6g polytetrafluoroethylene (PTFE) temperature rising reflux, system is added to be dropped after flowing back 5 hours in the reaction solution that step (1) is obtained
Temperature, 15g γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane and 10g isopropanols are added when the temperature of system is less than 40 DEG C,
Stirring obtains coating after 2 hours.
Comparative example 2
The coating is prepared via a method which to obtain:
(1) mixed liquor of 30g alkaline silica sols and 2.5g acetic acid is added in the reactor, and intensification reaches the temperature of system
Start that 60g MTESs are added dropwise at 60 DEG C, 2 hours completion of dropping control the temperature of reaction system during dropwise addition
It it is 60 DEG C, temperature rising reflux 1 hour after completion of dropping cools to less than 40 DEG C and obtains reaction solution;Wherein, alkaline silica sol
The a diameter of 12nm of grain;
(2) 0.02g carbon blacks are added in 15g γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, ultrasonic disperse 2
Hour obtains mixed liquor;
(3) mixed liquor and 10g isopropanols for adding step (2) to obtain in the reaction solution that step (1) is obtained, stirring 2 are small
When after obtain coating.
Comparative example 3
The coating is prepared via a method which to obtain:
(1) mixed liquor of 30g alkaline silica sols and 2.5g acetic acid is added in the reactor, and intensification reaches the temperature of system
Start that 60g MTESs are added dropwise at 60 DEG C, 2 hours completion of dropping control the temperature of reaction system during dropwise addition
It it is 60 DEG C, temperature rising reflux 1 hour after completion of dropping cools to less than 40 DEG C and obtains reaction solution;Wherein, alkaline silica sol
The a diameter of 12nm of grain;
(2) 6g polytetrafluoroethylene (PTFE), 0.02g carbon blacks, 15g γ-(2,3- epoxies are added in the reaction solution that step (1) is obtained
Third oxygen) propyl trimethoxy silicane and 10g isopropanols, stirring obtains coating after 2 hours.
Comparative example 4
The coating is prepared via a method which to obtain:
(1) mixed liquor of 30g alkaline silica sols and 2.5g acetic acid is added in the reactor, and intensification reaches the temperature of system
Start that 60g MTESs are added dropwise at 60 DEG C, 2 hours completion of dropping control the temperature of reaction system during dropwise addition
It it is 60 DEG C, temperature rising reflux 1 hour after completion of dropping cools to less than 40 DEG C and obtains reaction solution;Wherein, alkaline silica sol
The a diameter of 12nm of grain;
(2) added in the reaction solution that step (1) is obtained 15g γ-(oxygen of 2,3- epoxies third) propyl trimethoxy silicane and
10g isopropanols, stirring obtains coating after 2 hours.
Comparative example 5
The coating is prepared via a method which to obtain:
(1) mixed liquor of 30g alkaline silica sols and 2.5g acetic acid is added in the reactor, and intensification reaches the temperature of system
Start that 60g MTESs are added dropwise at 60 DEG C, 2 hours completion of dropping control the temperature of reaction system during dropwise addition
It it is 60 DEG C, temperature rising reflux 1 hour, cools and obtain reaction solution after completion of dropping;Wherein, alkaline silica sol particle diameter is
12nm;
(2) 0.1g carbon blacks are added in 15g γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, ultrasonic disperse 2 is small
When obtain mixed liquor;
(3) 6g polytetrafluoroethylene (PTFE) temperature rising reflux, system is added to be dropped after flowing back 5 hours in the reaction solution that step (1) is obtained
Temperature, the mixed liquor and 10g isopropanols for adding step (2) to obtain when the temperature of system is less than 40 DEG C, stirring is applied after 2 hours
Material.
Comparative example 6
The coating is prepared via a method which to obtain:
(1) mixed liquor of 30g alkaline silica sols and 2.5g acetic acid is added in the reactor, and intensification reaches the temperature of system
Start that 60g MTESs are added dropwise at 60 DEG C, 2 hours completion of dropping control the temperature of reaction system during dropwise addition
It it is 60 DEG C, temperature rising reflux 1 hour, cools and obtain reaction solution after completion of dropping;Wherein, alkaline silica sol particle diameter is
12nm;
(2) 0.001g carbon blacks are added in 15g γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, ultrasonic disperse 2
Hour obtains mixed liquor;
(3) 6g polytetrafluoroethylene (PTFE) temperature rising reflux, system is added to be dropped after flowing back 5 hours in the reaction solution that step (1) is obtained
Temperature, the mixed liquor and 10g isopropanols for adding step (2) to obtain when the temperature of system is less than 40 DEG C, stirring is applied after 2 hours
Material.
Performance detection:
Coating in embodiment 1-6 and comparative example 1-6 is prepared into wear-resistant coating on lucite surface.Table after paint spraying
The dry time is not less than 30min, is toasted in 80 DEG C -85 DEG C of environment after surface drying, and baking time is not less than 120min.To coating
Wear-resisting, scraping and wiping resistance performance is tested.
1. wearability:
Using《Determination of Abrasion Resistance for Coating Film (GB/T1768-79 (89))》With《Solid wooden compound floor (GB/T18103-
2000)》Both combine the wearability of detection surface of test piece.
Using abrasion instrument (JM-IV types, Shanghai modern environment project research institute), rotation friction rubber wheel method is used
(GB/T15102-1994 appendix As), respectively with the average value of coating quality loss (weight-loss method) after being ground through regulation grinding revolution,
Or represented in the two kinds of methods of average abrasive revolution (revolution method) needed for the same thickness coatings that wear and tear and evaluate wear-resisting
Property.
2. scratch resistance
2.1 scratch resistances (nail cut)
The surface nail of coating is scratched 10 and visually observes surface back and forth, evaluated according to following benchmark.
○:Scratch rear vestige to disappear, scratch resistance is high
△:A little vestige is remained after scratching, scratch resistance is somewhat low, but is had no problem in practicality
×:Vestige is remained after scratching, scratch resistance is low, problematic in practicality
2.2 scratch resistances (steel wool)
To the surface of coating, rubbed 10 with load 1.5kgf with steel wool (#0000) and visually observe surface back and forth, pressed
Evaluated according to following benchmark.
○:Hinder mark disappearance after friction, scratch resistance is high
△:Remained after friction and hinder mark a little, scratch resistance is somewhat low, but is had no problem in practicality
×:Remained after friction and hinder mark, scratch resistance is low, problematic in practicality
Wear-resisting, the scraping and wiping resistance performance of coating are shown in Table 1
The wearability and scratch resistance check experiment result of the coating of table 1
Not carbon black and polytetrafluoroethylene (PTFE), comparative example 1 are can be seen that in the coating of comparative example 4 by the test data in table 1
Coating in not carbon black, polytetrafluoroethylene (PTFE), raw material and the phase of embodiment 1 of the coating of comparative example 3 are free of in the coating of comparative example 2
Together, but preparation method is different, the consumption of carbon black is not fallen within scope of the present application in the coating of comparative example 5-6, right with above-mentioned
Ratio is compared, and the coating that the coating in the embodiment of the present application 1-6 is obtained has excellent wearability and scratch resistance.