CN110698709A - Light wear-resistant automobile side window glass and preparation method thereof - Google Patents
Light wear-resistant automobile side window glass and preparation method thereof Download PDFInfo
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- B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
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Abstract
The invention relates to the technical field of automobile window glass, and discloses light wear-resistant automobile side window glass and a preparation method thereofNano SiO of siloxane2And polycarbonate-polydimethylsiloxane copolymers. The preparation method comprises the following steps: firstly, injection molding the polycarbonate base layer by using a double-color injection mold, and then injection molding the PC/ABS black edge layer in the same mold; baking the polycarbonate base layer and the PC/ABS black edge layer to remove internal stress, and scrubbing the surface by using an alcohol solvent; and (5) spraying and drying to obtain the surface coating. The invention coats the modified coating on the polycarbonate base layer and the PC/ABS black edge layer surface, thereby greatly improving the wear resistance, weather resistance and hydrophobicity of the side window glass.
Description
Technical Field
The invention relates to the technical field of automobile window glass, in particular to light wear-resistant automobile side window glass and a preparation method thereof.
Background
With the continuous progress of society, the living standard of people is also continuously improved, the demand of automobiles is increased more than before, and the keeping quantity of automobiles is also increased more and more. With the policy of forcing automobile manufacturers to reduce automobile fuel consumption, the weight reduction of automobiles becomes an important breakthrough for large enterprises. According to statistics, the fuel consumption can be reduced by 0.6-1.0% when the weight of the automobile is reduced by 1%, and the energy consumption is closely related to the exhaust emission. Therefore, the light weight of the automobile has great significance for energy conservation and environmental protection. The weight reduction is already an important strategy in China, and more research institutions and the automobile industry focus on the weight reduction of automobiles.
Because Polycarbonate (PC) has excellent impact resistance, transparency and plasticity, the use of polycarbonate windows is an effective means for realizing light weight of automobiles, the automobiles can be lighter, the center of gravity of the automobiles is reduced, the energy consumption is reduced, and meanwhile, the high impact property of polycarbonate can be kept without crushing during rollover, so that the safety of personnel in the automobiles is improved. And the polycarbonate automobile window component can be used for increasing the curved surface modeling of the window according to streamline and aerodynamics and integrating functional structural members such as buckles, so that the matching problem among parts is reduced and the cost of the window component is reduced. Therefore, extensive research and attention has been directed to the use of polycarbonate windows to achieve weight reduction in automobiles, for example, a "lightweight window glass and a process for producing the same" disclosed in chinese patent document, publication No. CN103158501A, includes a polycarbonate plastic panel having a hardened film coated on both the inner and outer sides thereof. The light vehicle window glass is made of a polycarbonate plastic panel, the polycarbonate plastic panel is light in weight, the weight of the polycarbonate plastic panel with the same size is only equal to 1/2 weight of organic glass, and the light vehicle window glass has important significance for reducing the weight of a car body and reducing oil consumption.
However, the polycarbonate material has poor wear resistance, weather resistance and water repellency, so that the polycarbonate material directly used as the window glass has the problems of easy scratch generation, poor sealing property, incapability of preventing water and fog, influence on sight and the like. Therefore, a coating with the performances of wear resistance, weather resistance, hydrophobicity and the like needs to be coated on the surface of the polycarbonate glass, but the coating in the prior art is difficult to obviously improve the wear resistance, the weather resistance and the hydrophobicity of the polycarbonate glass at the same time, and the adhesive force of the coating on the polycarbonate glass is poor, so that the use performance is influenced.
Disclosure of Invention
The invention aims to overcome the problems that in the prior art, polycarbonate is directly used as vehicle window glass, the wear resistance, the weather resistance and the hydrophobicity are poor, the scratch is easy, the sealing performance is poor, the sight is influenced due to the fact that water and fog cannot be prevented, therefore, a coating needs to be coated on the surface of the polycarbonate glass, but the coating in the prior art is difficult to simultaneously and obviously improve the wear resistance, the weather resistance and the hydrophobicity of the polycarbonate glass, and the adhesion of the coating on the polycarbonate glass is poor, which affects the use performance, provides a light wear-resistant automobile side window glass and a preparation method thereof, the surface coating is coated on the polycarbonate substrate and the PC/ABS black edge layer, the coating has strong adhesive force with the resin layer, can obviously improve the wear resistance, weather resistance and hydrophobicity of the window glass, realizes the light weight of an automobile and simultaneously improves the service performance of the window glass.
In order to achieve the purpose, the invention adopts the following technical scheme:
the light wear-resistant automobile side window glass comprises a polycarbonate base layer, wherein a PC/ABS black edge layer is arranged on the periphery of one side of the polycarbonate base layer, surface coatings are coated on the surfaces of two sides of the polycarbonate base layer and the surface of the PC/ABS black edge layer, and the coating components of the surface coatings comprise a solvent and nano SiO with polydimethylsiloxane grafted on the surface2And polycarbonate-polydimethylsiloxaneAn alkylene oxide copolymer.
The side window glass adopts a polycarbonate substrate and a glass main body, and is provided with a PC/ABS black edge layer on the periphery, and the surface of the side window glass is coated with a surface coating. The polycarbonate substrate has good mechanical property, impact strength, temperature resistance and ultraviolet resistance, and light weight, and is beneficial to realizing light weight of an automobile. The PC/ABS black edge layer combines the characteristics of polycarbonate and polyacrylonitrile, has good formability and impact strength, can absorb heat, enables the vehicle window to be heated uniformly, and prevents glass from cracking; and can cover joint strip, block sunshine and penetrate joint strip directly, prevent that adhesive tape and glue are ageing. However, the polycarbonate substrate has poor wear resistance, weather resistance and hydrophobicity, and does not meet the use requirements of vehicle windows, so the surface coatings are coated on the two side surfaces of the invention.
Polydimethylsiloxane is a common organic silicon coating material, and has very high hydrophobicity and very low surface energy, so that the hydrophobicity of the coating can be improved, the adhesion strength of pollutants on the surface of the coating is reduced, and the glass has waterproof and antifouling performances. Therefore, the polydimethylsiloxane is added into the coating of the surface coating, so that the coating has good hydrophobicity. However, since the polydimethylsiloxane is composed of Si-O bonds, the bond energy of the Si-O bonds is low as compared with that of C-C bonds, and thus the mechanical properties of the polydimethylsiloxane are low as compared with other polymers having C-C as a main chain. And the nonpolar methyl group is wrapped on the outer side of the main chain, so that the polydimethylsiloxane presents strong repulsion to the polar functional group, and the polydimethylsiloxane coating has poor adhesion to a polycarbonate base layer containing the polar functional group and a PC/ABS layer and is easy to fall off. Therefore, the polydimethylsiloxane is modified to prepare the polycarbonate-polydimethylsiloxane copolymer, so that on one hand, the rejection of the polydimethylsiloxane to the polar functional groups on the surface of the polycarbonate is improved, and the adhesive force of the coating on the surfaces of the polycarbonate base layer and the PC/ABS layer is improved; on the other hand, the polycarbonate-polydimethylsiloxane copolymer has outstanding weather resistance, heat resistance and flame retardance, and can effectively improve the performance of the coating.
Meanwhile, the invention also adds inorganic filler in the coating,adding nano SiO2Can effectively improve the wear resistance and the weather resistance of the coating, but the nano SiO is directly added2Due to the large specific surface area and the large surface energy, the nano particles are easy to agglomerate, and the uniform dispersion of the nano particles in the coating material is influenced; and as a nano SiO of an inorganic material2Poor compatibility with organic polycarbonate-polydimethylsiloxane copolymers does not allow the coatings to achieve the desired properties. Therefore, the invention grafts the polydimethylsiloxane on the nano SiO2Surface, reduced nano SiO2The surface energy of the nano SiO is improved, the dispersity is improved, and the grafted nano SiO is2Has good compatibility with the polycarbonate-polydimethylsiloxane copolymer, thereby leading the coating to have good performance.
Therefore, the invention coats nano SiO comprising surface grafted polydimethylsiloxane on the surface of the polycarbonate base layer2And the surface coating of the polycarbonate-polydimethylsiloxane copolymer reduces the weight of the car window glass, so that the car window has good wear resistance, weather resistance and hydrophobicity, and meets the use requirements.
Preferably, the preparation method of the coating of the surface coating comprises the following steps:
(A) mixing nano SiO2Dispersing in ethanol, adding into nanometer SiO25g of gamma-aminopropyltriethoxysilane and 1-3 drops of triethylamine in the proportion of (8-10mL), stirring for reaction for 5-8h, centrifugally separating, washing the product with ethanol, acetone and tetrahydrofuran in sequence, dispersing the product in tetrahydrofuran, adding nano SiO2The mass ratio is (2-3): 1 glutaric anhydride, stirring for 5-8h, centrifuging, washing with NaCl solution repeatedly, and drying to obtain carboxylated nano SiO2；
(B) Mixing the following components in percentage by mass (20-30): octamethylcyclotetrasiloxane of 1 and (CH)3)4NOH is mixed and is subjected to dehydration reaction for 2-3h under the negative pressure condition of 50-70 ℃ to obtain the silicon alkoxide catalyst, and the weight ratio of the silicon alkoxide catalyst to the silicon alkoxide catalyst is 100: (0.2-0.3) octamethylcyclotetrasiloxane and 1, 3-bis- (2-aminoethylaminomethyl) tetramethyldisilane, stirring uniformly, adding the mixture according to the mass ratio of (0.7-0.8):100, reacting at 80-90 ℃ for 4-6h, and removing low-boiling-point substances at 140-150 ℃ under negative pressure to obtain the diamino terminated polydimethylsiloxane;
(C) the carboxylated nano SiO prepared in the step (A) is added2Dispersing in tetrahydrofuran, adding dicyclohexylcarbodiimide and the diamino terminated polydimethylsiloxane prepared in the step (B), reacting for 20-30h at 75-85 ℃, repeatedly washing the obtained product with methanol and tetrahydrofuran, and drying at 60-70 ℃ to obtain the nano SiO with the surface grafted with the polydimethylsiloxane2Carboxylated nano SiO2The mass ratio of dicyclohexylcarbodiimide to diamino end-capped polydimethylsiloxane is 100: (15-20): (80-90); (D) mixing the components in a mass ratio of 1: (60-70): (5-8) mixing polydimethylsiloxane, diphenyl carbonate and magnesium chloride, reacting for 10-20min under the protection of 150-180 ℃ inert gas, cooling to room temperature, adding bisphenol A with the same mass as the diphenyl carbonate, reacting for 2-3h under the protection of 170-250 ℃ inert gas, adding the product into dichloromethane, repeatedly washing with absolute ethyl alcohol, filtering and drying to obtain a polycarbonate-polydimethylsiloxane copolymer;
(E) nano SiO of surface grafted polydimethylsiloxane2And the polycarbonate-polydimethylsiloxane copolymer auxiliary agent is dispersed in a solvent to obtain the coating, and the nano SiO of the polydimethylsiloxane is grafted on the surface of the coating2The mass ratio of the polycarbonate-polydimethylsiloxane copolymer to the polycarbonate-polydimethylsiloxane copolymer is (1-5): 100, the concentration of the polycarbonate-polydimethylsiloxane copolymer is 50-100 g/L.
In the step (A), firstly, the nano SiO is2Reacting with gamma-aminopropyl triethoxysilane, in the presence of triethylamine as promoter, in the presence of nano SiO2Amino is introduced to the surface to obtain aminated nano SiO2(ii) a Then aminated nano SiO2Reacting with glutaric anhydride to obtain carboxylated nano SiO2. In the step (B), through the ring-opening reaction of octamethylcyclotetrasiloxane, 1, 3-bis- (2-aminoethylaminomethyl) tetramethyldisilane is added to obtain the diamino terminated polydimethylsiloxane. Then, through the step (C), the nano SiO2The carboxyl groups on the surface may be reacted with polydimethyl siliconThe amino groups at the two ends of the siloxane are subjected to condensation reaction, so that the polydimethylsiloxane is grafted on the nano SiO2Surface grafting polydimethylsiloxane to obtain nano SiO2. Step (D) is to prepare polycarbonate-polydimethylsiloxane block copolymer through melt transesterification, and finally, step (E) is to graft nano SiO of polydimethylsiloxane on the surface2Mixing with polycarbonate-polydimethylsiloxane copolymer and dispersing in solvent to obtain coating material containing nano SiO2Has good dispersibility and good compatibility with the polycarbonate-polydimethylsiloxane copolymer.
Preferably, the solvent in the dope for the top coat is cyclohexane. Cyclohexane can effectively dissolve the polycarbonate-polydimethylsiloxane copolymer, and the content of polydimethylsiloxane in the dried coating surface layer can meet the requirement of the car window on hydrophobic performance.
Preferably, the paint of the surface coating also comprises an antifoaming agent and a leveling agent, and the addition amount of the antifoaming agent and the leveling agent is 0.1-0.5 g/L. The coating performance of the coating can be improved by adding a proper amount of defoaming agent and leveling agent into the coating, so that the performance of the coated coating is improved.
Preferably, the thickness of the polycarbonate substrate layer is 3-8mm, the thickness of the PC/ABS black border layer is 2-3mm, and the thickness of the surface coating layer is 10-20 μm. The weight, mechanical property, shock resistance, temperature resistance, ultraviolet resistance, wear resistance, weather resistance and hydrophobicity of the side window glass can all meet the use requirements by adopting the thickness of each layer.
The invention also provides a preparation method of the light wear-resistant automobile side window glass, which comprises the following steps:
(1) adding the dried polycarbonate granules and black PC/ABS granules into a double-color injection molding machine, firstly performing injection molding on a polycarbonate base layer by using a double-color injection mold, and then performing injection molding on a PC/ABS black edge layer in the same mold;
(2) baking the polycarbonate base layer and the PC/ABS black border layer obtained by injection molding to remove internal stress, and scrubbing the surface of the polycarbonate base layer and the PC/ABS black border layer with the internal stress by using an alcohol solvent;
(3) and (3) coating the paint of the surface coating on the surfaces of the polycarbonate base layer and the PC/ABS black edge layer, baking, and cooling to room temperature to obtain the side window glass.
In the step (1), the polycarbonate granules and the black PC/ABS granules are baked to remove moisture, and then the polycarbonate base layer and the PC/ABS black edge layer are subjected to injection molding, so that double-curved complex shapes and the like can be realized, functional structural parts are integrated, the method is simple, and the operation flow is convenient. Before the surface coating is coated, internal stress is removed through the step (2), and the surface grease, ash layer and other dirt are scrubbed by using an alcohol solvent, so that the adhesive force of the coating is improved. And (4) finally, the surface coating is sprayed and coated in the step (3), so that the wear resistance, weather resistance and hydrophobicity of the side window glass are effectively improved.
Preferably, the drying temperature of the polycarbonate granules and the black PC/ABS granules in the step (1) is 95-105 ℃, and the drying time is 3-5 h. With this temperature and time, the moisture in the polycarbonate pellets and black PC/ABS pellets can be sufficiently removed without decomposition denaturation of the pellets.
Preferably, the baking temperature in the step (2) is 115-125 ℃, and the baking time is 25-35 min. The internal stress of the polycarbonate substrate and the PC/ABS black edge layer can be effectively removed at the temperature and in the time, and the adhesive force of the coating is improved.
Preferably, the curtain coating in the step (3) is carried out in a 1000-grade clean room, the baking temperature is 120-. Under the baking temperature and time, the surface coating can be effectively cured, and the coating is ensured to have good performance.
Therefore, the invention has the following beneficial effects: the polycarbonate-polydimethylsiloxane copolymer is used in the surface coating, so that on one hand, the repulsion of polydimethylsiloxane to the polar functional groups on the surface of polycarbonate is improved, and the adhesive force of the coating on the surfaces of a polycarbonate base layer and a PC/ABS layer is improved; on the other hand, the polycarbonate-polydimethylsiloxane copolymer has outstanding weather resistance, heat resistance and flame retardance, and can effectively improve the performance of the coating; and nano SiO with the surface grafted with polydimethylsiloxane is added2Improves the wear resistance and the weather resistance of the coating and improves the nano SiO2Dispersibility and compatibility in polycarbonate-polydimethylsiloxane copolymers. The prepared side window glass has light weight, good mechanical property, good impact strength, good temperature resistance, good ultraviolet resistance, good wear resistance, good weather resistance and good hydrophobicity.
Drawings
FIG. 1 is a schematic diagram of an embodiment of the present invention.
In the figure: 1 polycarbonate substrate, 2PC/ABS black border layer and 3 surface coating.
Detailed Description
The invention is further described with reference to the following detailed description and accompanying drawings.
Example 1:
as shown in figure 1, the light wear-resistant automobile side window glass comprises a polycarbonate base layer 1 with the thickness of 5mm, a PC/ABS black border layer 2 with the thickness of 2.5mm is arranged on the periphery of one side of the polycarbonate base layer, and surface coatings 3 with the thickness of 15 mu m are coated on the two side surfaces of the polycarbonate base layer and the surface of the PC/ABS black border layer.
The preparation method of the paint used for the surface coating comprises the following steps:
(A) mixing nano SiO2Dispersing in ethanol, adding into nanometer SiO25g of gamma-aminopropyltriethoxysilane and 2 drops of triethylamine in a ratio of 9mL, stirring for 6 hours, centrifugally separating, washing the product twice with ethanol, acetone and tetrahydrofuran in sequence, dispersing the product in tetrahydrofuran, adding the product and nano SiO2The mass ratio is 2.5: 1 glutaric anhydride, stirring for 6 hours, centrifugally separating, repeatedly washing with 0.1mol/L NaCl solution, and drying to obtain carboxylated nano SiO2；
(B) And (2) mixing the components in a mass ratio of 25: octamethylcyclotetrasiloxane of 1 and (CH)3)4Mixing NOH, and carrying out dehydration reaction for 2.5h at the temperature of 60 ℃ under negative pressure to obtain a silicon alkoxide catalyst, wherein the mass ratio of the NOH to the silicon alkoxide catalyst is 100: 0.25 of octamethylcyclotetrasiloxane and 1, 3-bis- (2-aminoethylaminomethyl) tetramethyldisilane, uniformly stirring, and adding a mixture of octamethylcyclotetrasiloxane and 1, 3-bis- (2-aminoethylaminomethyl) tetramethyldisilane in a mass ratio of 0.75: 100 silicon alkoxide catalyst reacts for 5 hours at 85 ℃, and then low-boiling-point substances are removed under the negative pressure of 145 ℃ to obtain the diamino terminated polydimethylsiloxane；
(C) The carboxylated nano SiO prepared in the step (A) is added2Dispersing in tetrahydrofuran, adding dicyclohexylcarbodiimide and the diamino end-capped polydimethylsiloxane prepared in the step (B), reacting for 25h at 80 ℃, repeatedly washing the obtained product with methanol and tetrahydrofuran, and drying at 65 ℃ to obtain the nano SiO of the surface grafted polydimethylsiloxane2Carboxylated nano SiO2The mass ratio of dicyclohexylcarbodiimide to diamino end-capped polydimethylsiloxane is 100:18: 85;
(D) mixing the components in a mass ratio of 1: 65: 7, mixing polydimethylsiloxane, diphenyl carbonate and magnesium chloride, reacting for 15min at 170 ℃ under the protection of inert gas, cooling to room temperature, adding bisphenol A with the same mass as the diphenyl carbonate, reacting for 2.5h at 200 ℃ under the protection of inert gas, adding the product into dichloromethane, repeatedly washing with absolute ethyl alcohol, filtering and drying to obtain a polycarbonate-polydimethylsiloxane copolymer;
(E) nano SiO of surface grafted polydimethylsiloxane2And polycarbonate-polydimethylsiloxane copolymer is dispersed in cyclohexane, 0.2g/L of German BYK defoaming agent BYK-052 and 0.2g/L of German byK flatting agent BYK-331 are added to obtain coating, and nano SiO of polydimethylsiloxane is grafted on the surface of the coating2The mass ratio of the polycarbonate-polydimethylsiloxane copolymer to the polycarbonate-polydimethylsiloxane copolymer is 3: 100, the concentration of the polycarbonate-polydimethylsiloxane copolymer was 70 g/L.
The preparation method of the light wear-resistant automobile side window glass comprises the following steps:
(1) drying the vehicle window-grade polycarbonate granules and the black PC/ABS granules in a drying barrel at 100 ℃ for 4 hours, and removing the moisture of the granules; adding the dried polycarbonate granules and black PC/ABS granules into a double-color injection molding machine, performing first injection by using a double-color injection mold, performing injection molding on a polycarbonate base layer, and performing second injection by horizontally rotating the mold, thereby performing injection molding on the PC/ABS black side layer;
(2) placing the polycarbonate base layer and the PC/ABS black edge layer obtained by injection molding on a tool support, removing internal stress in a drying tunnel at 120 ℃ for 30min, and scrubbing dirt such as surface grease, ash layer and the like by using ethanol;
(3) and in a 1000-grade clean room, spraying the coating of the surface coating on the surfaces of the polycarbonate base layer and the PC/ABS black side layer, baking for 35min in an oven at 125 ℃, and cooling to room temperature to obtain the side window glass.
Example 2:
the light wear-resistant automobile side window glass comprises a polycarbonate base layer with the thickness of 3mm, a PC/ABS black border layer with the thickness of 2mm is arranged on the periphery of one side of the polycarbonate base layer, and surface coatings with the thickness of 10 mu m are coated on the surfaces of the two sides of the polycarbonate base layer and the surface of the PC/ABS black border layer.
The preparation method of the paint used for the surface coating comprises the following steps:
(A) mixing nano SiO2Dispersing in ethanol, adding into nanometer SiO25g of gamma-aminopropyltriethoxysilane and 1 drop of triethylamine in a ratio of 8mL to 5g, stirring for 5 hours, centrifugally separating, washing the product twice with ethanol, acetone and tetrahydrofuran in sequence, dispersing the product in tetrahydrofuran, and adding nano SiO2The mass ratio is 2: 1 glutaric anhydride, stirring for 5 hours, centrifugally separating, repeatedly washing with 0.1mol/L NaCl solution, and drying to obtain carboxylated nano SiO2；
(B) And (2) mixing the following components in percentage by mass: octamethylcyclotetrasiloxane of 1 and (CH)3)4Mixing NOH, and carrying out dehydration reaction for 3h at the temperature of 50 ℃ under negative pressure to obtain a silicon alkoxide catalyst, wherein the mass ratio of the NOH to the silicon alkoxide catalyst is 100: 0.2 of octamethylcyclotetrasiloxane and 1, 3-bis- (2-aminoethylaminomethyl) tetramethyldisilane, uniformly stirring, and adding a mixture of octamethylcyclotetrasiloxane and 1, 3-bis- (2-aminoethylaminomethyl) tetramethyldisilane in a mass ratio of 0.7: reacting 100 silicon alkoxide catalyst at 80 ℃ for 4h, and removing low-boiling-point substances at 140 ℃ under negative pressure to obtain diamino terminated polydimethylsiloxane;
(C) the carboxylated nano SiO prepared in the step (A) is added2Dispersing in tetrahydrofuran, adding dicyclohexylcarbodiimide and the diamino terminated polydimethylsiloxane prepared in the step (B), reacting for 20h at 75 ℃, repeatedly washing the obtained product with methanol and tetrahydrofuran, and drying at 60 ℃ to obtain the nano SiO of the surface grafted polydimethylsiloxane2Carboxylated nano SiO2Dicyclohexyl carbonThe mass ratio of the diimine to the diamino terminated polydimethylsiloxane is 100:15: 80;
(D) mixing the components in a mass ratio of 1: 60: 5, mixing polydimethylsiloxane, diphenyl carbonate and magnesium chloride, reacting for 20min under the protection of 150 ℃ inert gas, cooling to room temperature, adding bisphenol A with the same mass as the diphenyl carbonate, reacting for 3h under the protection of 170 ℃ inert gas, adding the product into dichloromethane, repeatedly washing with absolute ethyl alcohol, filtering and drying to obtain a polycarbonate-polydimethylsiloxane copolymer;
(E) nano SiO of surface grafted polydimethylsiloxane2And polycarbonate-polydimethylsiloxane copolymer is dispersed in cyclohexane, 0.1g/L of German BYK defoaming agent BYK-052 and 0.1g/L of German byK flatting agent BYK-331 are added to obtain coating, and nano SiO of polydimethylsiloxane is grafted on the surface of the coating2The mass ratio of the polycarbonate-polydimethylsiloxane copolymer to the polycarbonate-polydimethylsiloxane copolymer is 1: 100, the concentration of the polycarbonate-polydimethylsiloxane copolymer is 50 g/L.
The preparation method of the light wear-resistant automobile side window glass comprises the following steps:
(1) drying the vehicle window-grade polycarbonate granules and the black PC/ABS granules in a drying barrel at the temperature of 95 ℃ for 5 hours, and removing the moisture of the granules; adding the dried polycarbonate granules and black PC/ABS granules into a double-color injection molding machine, performing first injection by using a double-color injection mold, performing injection molding on a polycarbonate base layer, and performing second injection by horizontally rotating the mold, thereby performing injection molding on the PC/ABS black side layer;
(2) placing the polycarbonate base layer and the PC/ABS black edge layer obtained by injection molding on a tool support, removing internal stress in a drying tunnel at 115 ℃ for 35min, and scrubbing dirt such as surface grease, ash layer and the like by using ethanol;
(3) and in a 1000-grade clean room, spraying the coating of the surface coating on the polycarbonate base layer and the surface of the PC/ABS black side layer, baking for 40min in an oven at 120 ℃ after spraying, and cooling to room temperature to obtain the side window glass.
Example 3:
the light wear-resistant automobile side window glass comprises a polycarbonate base layer with the thickness of 8mm, a PC/ABS black border layer with the thickness of 3mm is arranged on the periphery of one side of the polycarbonate base layer, and surface coatings with the thickness of 20 mu m are coated on the surfaces of the two sides of the polycarbonate base layer and the surface of the PC/ABS black border layer.
The preparation method of the paint used for the surface coating comprises the following steps:
(A) mixing nano SiO2Dispersing in ethanol, adding into nanometer SiO25g of gamma-aminopropyltriethoxysilane and 3 drops of triethylamine in a proportion of 10mL, stirring for 8 hours, centrifugally separating, washing the product twice with ethanol, acetone and tetrahydrofuran in sequence, dispersing the product in tetrahydrofuran, adding the product and nano SiO2The mass ratio is 3: 1 glutaric anhydride, stirring for 8 hours, centrifugally separating, repeatedly washing with 0.1mol/L NaCl solution, and drying to obtain carboxylated nano SiO2；
(B) And (3) mixing the following components in percentage by mass: octamethylcyclotetrasiloxane of 1 and (CH)3)4Mixing NOH, and carrying out dehydration reaction for 2h at 70 ℃ under negative pressure to obtain a silicon alkoxide catalyst, wherein the mass ratio of the NOH to the silicon alkoxide catalyst is 100: 0.3 of octamethylcyclotetrasiloxane and 1, 3-bis- (2-aminoethylaminomethyl) tetramethyldisilane, uniformly stirring, and adding the mixture, wherein the mass ratio of the mixture to the octamethylcyclotetrasiloxane is 0.8: reacting 100 parts of silicon alkoxide catalyst at 90 ℃ for 6 hours, and removing low-boiling-point substances at 150 ℃ under negative pressure to obtain diamino terminated polydimethylsiloxane;
(C) the carboxylated nano SiO prepared in the step (A) is added2Dispersing in tetrahydrofuran, adding dicyclohexylcarbodiimide and the diamino terminated polydimethylsiloxane prepared in the step (B), reacting for 30h at 85 ℃, repeatedly washing the obtained product with methanol and tetrahydrofuran, and drying at 70 ℃ to obtain the nano SiO of the surface grafted polydimethylsiloxane2Carboxylated nano SiO2The mass ratio of dicyclohexylcarbodiimide to diamino end-capped polydimethylsiloxane is 100:20: 90;
(D) mixing the components in a mass ratio of 1: 70: 8, mixing polydimethylsiloxane, diphenyl carbonate and magnesium chloride, reacting for 10min at 180 ℃ under the protection of inert gas, cooling to room temperature, adding bisphenol A with the same mass as the diphenyl carbonate, reacting for 2h at 250 ℃ under the protection of inert gas, adding the product into dichloromethane, repeatedly washing with absolute ethyl alcohol, filtering and drying to obtain a polycarbonate-polydimethylsiloxane copolymer;
(E) nano SiO of surface grafted polydimethylsiloxane2And polycarbonate-polydimethylsiloxane copolymer is dispersed in cyclohexane, 0.5g/L of German BYK defoaming agent BYK-052 and 0.5g/L of German byK flatting agent BYK-331 are added to obtain coating, and nano SiO of polydimethylsiloxane is grafted on the surface of the coating2The mass ratio of the polycarbonate-polydimethylsiloxane copolymer to the polycarbonate-polydimethylsiloxane copolymer is 5: 100, the concentration of the polycarbonate-polydimethylsiloxane copolymer is 100 g/L.
The preparation method of the light wear-resistant automobile side window glass comprises the following steps:
(1) drying the vehicle window-grade polycarbonate granules and the black PC/ABS granules in a drying barrel at 105 ℃ for 3 hours, and removing the moisture of the granules; adding the dried polycarbonate granules and black PC/ABS granules into a double-color injection molding machine, performing first injection by using a double-color injection mold, performing injection molding on a polycarbonate base layer, and performing second injection by horizontally rotating the mold, thereby performing injection molding on the PC/ABS black side layer;
(2) placing the polycarbonate base layer and the PC/ABS black edge layer obtained by injection molding on a tool support, removing internal stress in a drying tunnel at 125 ℃ for 25min, and scrubbing dirt such as surface grease, ash layer and the like by using ethanol;
(3) and in a 1000-grade clean room, spraying the coating of the surface coating on the polycarbonate base layer and the surface of the PC/ABS black side layer, baking for 30min in an oven at 130 ℃ after spraying, and cooling to room temperature to obtain the side window glass.
Comparative example 1:
comparative example 1 differs from example 1 in that the polycarbonate base layer and the PC/ABS black border layer surfaces were not coated with a surface coating, and the rest was the same as in example 1.
The side window glasses prepared in the above examples and comparative examples were tested for abrasion resistance, weather resistance and water repellency, and the results are shown in table 1.
Abrasion resistance sections (100mm x 100mm) of the specimens were subjected to a 500 cycle test using a Taber abrasion tester under CS-10F abrasion wheel and 500g load.haze difference (△ Haze) was calculated using transmission Haze meter BYK 4775 to test the front and back Haze values of the specimens according to the abrasion resistance test standard of ECE R43.
Weather resistance: the side window glass of the present invention was tested using a xenon lamp weathering chamber (UV-A) according to SAE J576.
Hydrophobicity: the side window glass of the present invention was subjected to hydrophobicity testing using a contact angle tester.
Table 1: abrasion resistance, weather resistance and hydrophobicity.
| Numbering | △Haze | Weather resistance | Contact angle |
| Example 1 | 2％ | 4515kJ/m2 | 102.4° |
| Example 2 | 5％ | 4537kJ/m2 | 101.1° |
| Example 3 | 3％ | 4551kJ/m2 | 101.5° |
| Comparative example 1 | 30％ | 550kJ/m2 | 80.2° |
As can be seen from Table 1, the abrasion resistance, weather resistance and water repellency of the side window glass prepared by the method of the invention in examples 1-3 are all obviously improved compared with those of comparative example 1 without coating a surface coating, and the use requirements of the side window glass can be met.
Claims (9)
1. The light wear-resistant automobile side window glass is characterized by comprising a polycarbonate base layer, wherein a PC/ABS black edge layer is arranged around one side of the polycarbonate base layer, surface coatings are coated on the surfaces of two sides of the polycarbonate base layer and the surface of the PC/ABS black edge layer, and the coating components of the surface coatings comprise a solvent and nano SiO with polydimethylsiloxane grafted on the surface2And polycarbonate-polydimethylsiloxane copolymers.
2. A light weight, wear resistant automotive side window glass as claimed in claim 1, wherein said surface coating paint is prepared by a method comprising the steps of:
(A) mixing nano SiO2Dispersing in ethanol, adding into nanometer SiO25g of gamma-aminopropyltriethoxysilane and 1-3 drops of triethylamine in the proportion of (8-10mL), stirring for reaction for 5-8h, centrifugally separating, washing the product with ethanol, acetone and tetrahydrofuran in sequence, dispersing the product in tetrahydrofuran, adding nano SiO2The mass ratio is (2-3): 1 glutaric anhydride, stirring for 5-8h, centrifuging, washing with NaCl solution repeatedly, and drying to obtain carboxylated nano SiO2；
(B) Mixing the following components in percentage by mass (20-30): octamethylcyclotetrasiloxane of 1 and (CH)3)4NOH is mixed and is subjected to dehydration reaction for 2-3h under the negative pressure condition of 50-70 ℃ to obtain the silicon alkoxide catalyst, and the weight ratio of the silicon alkoxide catalyst to the silicon alkoxide catalyst is 100: (0.2-0.3) Octamethylcyclotetrasiloxane and 1, 3-bis- (2-aminoethylaminomethyl) tetramethylMixing disilane, stirring uniformly, adding the mixture and octamethylcyclotetrasiloxane according to the mass ratio of (0.7-0.8): 100, reacting at 80-90 ℃ for 4-6h, and removing low-boiling-point substances at 140-150 ℃ under negative pressure to obtain the diamino terminated polydimethylsiloxane;
(C) the carboxylated nano SiO prepared in the step (A) is added2Dispersing in tetrahydrofuran, adding dicyclohexylcarbodiimide and the diamino terminated polydimethylsiloxane prepared in the step (B), reacting for 20-30h at 75-85 ℃, repeatedly washing the obtained product with methanol and tetrahydrofuran, and drying at 60-70 ℃ to obtain the nano SiO with the surface grafted with the polydimethylsiloxane2Carboxylated nano SiO2The mass ratio of dicyclohexylcarbodiimide to diamino end-capped polydimethylsiloxane is 100: (15-20): (80-90);
(D) mixing the components in a mass ratio of 1: (60-70): (5-8) mixing polydimethylsiloxane, diphenyl carbonate and magnesium chloride, reacting for 10-20min under the protection of 150-180 ℃ inert gas, cooling to room temperature, adding bisphenol A with the same mass as the diphenyl carbonate, reacting for 2-3h under the protection of 170-250 ℃ inert gas, adding the product into dichloromethane, repeatedly washing with absolute ethyl alcohol, filtering and drying to obtain a polycarbonate-polydimethylsiloxane copolymer;
(E) nano SiO of surface grafted polydimethylsiloxane2And polycarbonate-polydimethylsiloxane copolymer is dispersed in a solvent to obtain the coating, and nano SiO of polydimethylsiloxane is grafted on the surface of the coating2The mass ratio of the polycarbonate-polydimethylsiloxane copolymer to the polycarbonate-polydimethylsiloxane copolymer is (1-5): 100, and the concentration of the polydimethylsiloxane copolymer is 50-100 g/L.
3. A light weight, abrasion resistant automotive side window glass according to claim 1 or 2, wherein the solvent in the paint of said surface coating is cyclohexane.
4. A light weight, wear resistant automotive side window glass as claimed in claim 1 or 2, wherein the paint of said surface coating further comprises an antifoaming agent and a leveling agent, and the addition amount of the antifoaming agent and the leveling agent is 0.1-0.5 g/L.
5. The light-weight wear-resistant automobile side window glass as claimed in claim 1, wherein the thickness of the polycarbonate substrate layer is 3-8mm, the thickness of the PC/ABS black border layer is 2-3mm, and the thickness of the surface coating layer is 10-20 μm.
6. A method for preparing a light-weight wear-resistant automobile side window glass as claimed in any one of claims 1 to 5, which is characterized by comprising the following steps:
(1) adding the dried polycarbonate granules and black PC/ABS granules into a double-color injection molding machine, firstly performing injection molding on a polycarbonate base layer by using a double-color injection mold, and then performing injection molding on a PC/ABS black edge layer in the same mold;
(2) baking the polycarbonate base layer and the PC/ABS black border layer obtained by injection molding to remove internal stress, and scrubbing the surface of the polycarbonate base layer and the PC/ABS black border layer with the internal stress by using an alcohol solvent;
(3) and (3) coating the paint of the surface coating on the surfaces of the polycarbonate base layer and the PC/ABS black edge layer, baking, and cooling to room temperature to obtain the side window glass.
7. The method for preparing the light-weight wear-resistant automobile side window glass as claimed in claim 6, wherein the drying temperature of the polycarbonate granules and the black PC/ABS granules in the step (1) is 95-105 ℃, and the drying time is 3-5 h.
8. The method for preparing a light-weight wear-resistant automobile side window glass as claimed in claim 6, wherein the baking temperature in step (2) is 115 ℃ and 125 ℃, and the baking time is 25-35 min.
9. The method for preparing the light wear-resistant automobile side window glass as claimed in claim 6, wherein the spraying in the step (3) is carried out in a 1000-grade clean room, the baking temperature is 120-130 ℃, and the baking time is 30-40 min.
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