CN115926553B - High-permeability scratch-resistant automobile matte varnish and preparation method thereof - Google Patents
High-permeability scratch-resistant automobile matte varnish and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of automobile coatings, and particularly relates to a high-permeability scratch-resistant automobile matte varnish and a preparation method thereof. The invention provides a high-permeability scratch-resistant automobile matte varnish, which comprises the following components in percentage by mass: 10-15% of butyl acetate, 5-10% of propylene glycol methyl ether acetate, 5-6% of cyclohexanone, 4-5% of dispersing agent, 40-63.2% of acrylic resin, 8-12% of matte powder, 3-6% of PMMA powder, 0.1-1.0% of flatting agent, 0.1-1.0% of fumed silica, 0.5-1.0% of ultraviolet absorbent, 1-2% of scratch-resistant wear-resistant agent and 0.1-1.0% of organosilicon surface slipping auxiliary agent. The high-permeability scratch-resistant automobile matte varnish provided by the invention has the advantages of high film hardness, strong surface scratch resistance, excellent wear resistance, higher permeability and smooth hand feeling on the surface of the film.
Description
Technical Field
The invention belongs to the technical field of automobile coatings, and particularly relates to a high-permeability scratch-resistant automobile matte varnish and a preparation method thereof.
Background
The automobile is an efficient and convenient transportation tool, and has extremely high popularity because of the advantages of compactness, flexibility, strong road adaptability and the like. Meanwhile, the updating frequency of the automobile is high, the purchasing capability of people is high, and the demand of the automobile is extremely large. In a market environment with complex brands, good appearance is a primary choice of people on the premise of similar service performance of different vehicles. The varnish film layer is used as the last procedure of the outer surface coating operation, and plays a key role in corrosion resistance and gloss fullness. The varnish film layer has good adhesive force, corrosion resistance, good fullness, high gloss and other excellent characteristics.
Automotive varnishes are largely divided into two categories: acrylic system varnishes and polyurethane system varnishes. The polyurethane system varnish has excellent mechanical properties, but has poor weather resistance, and is easy to lose light, fade and even pulverize after outdoor use for one year; the acrylic varnish has excellent mechanical properties and strong weather resistance, and is most widely applied to automobile coating. Acrylic resins are polymers based on (meth) acrylic acid and its lipids, formed by polymerizing other substances. Acrylate monomers were found as early as Joseph Redtenbacher in the 40 th 19 th century. After that, tollen and Carpray found that acrylate monomers could polymerize, and therefore, they have received increasing attention, and the study of the structure and properties of acrylic polymers has been continued. The invention of the preparation technology of the acrylic acid monomer is invented by German chemist OttoRohm in the 20 th century, and the industrial production process of the acrylic acid ester monomer is truly researched. In 1930, the Bo Namen chemical industry (ICI) and dupont (Du pont) applied acrylic coatings successively to automotive coatings.
The varnish has a high gloss and a matte, and the matte varnish is favored in the market because of the elegant and drastic decorative effect of the coating. The matt varnish mainly comprises matting powder, synthetic resin, solvent and additive. The vehicle with the coating being the matte varnish has no traditional glaring and smooth appearance like a new vehicle, the glossiness of the matte varnish is very low, the whole vehicle can be more internal-astringed, and the vehicle is low in tone and luxury. Along with the diversified demands of users on the appearance of the paint surface, the paint surface with matte texture gradually enters the public field of view, and the matte varnish is also generated due to the uniform and unique paint surface effect, so that the paint surface is favored by more consumers. However, scratches and scratches on the paint surface using the matte varnish are difficult to repair, and forced repair may eventually lead to an inconsistent paint surface appearance. Therefore, how to improve the scratch resistance of the matt varnish becomes a great difficulty for automobile coatings.
Chinese patent application CN114806303a discloses a varnish suitable for one-time spray coating of a vehicle body to form a film and a preparation method thereof, wherein the varnish comprises, by mass: 33.0% -40.0% of main resin, 8.0% -12.0% of functional resin A, 6.0% -10.0% of functional resin B, 20.0% -30.0% of cross-linking agent, 0.3% -0.8% of leveling agent, 0.1% -0.5% of anti-aging agent, 3.0% -6.0% of rheological additive, 5.0% -8.0% of solvent A and 4.0% -8.0% of solvent B; the main resin is thermosetting hydroxy acrylic resin, the functional resin A is organic-inorganic silicon hybrid resin, and the functional resin B is urethane oligomer, so that the problem that sagging and prickly heat points easily occur in varnish spraying after the spraying process parameters are adjusted can be solved. Chinese patent application CN102040907a discloses an ultraviolet woodware matte varnish free of residual pungent odor after curing, which comprises the following components in weight percentage: 35-50% of modified acrylic ester, 35-45% of functional monomer, 0.1-0.3% of defoaming agent, 0.3-1% of flatting agent, 0-11% of flatting agent, 5-7% of photoinitiator and 0-1.0% of dispersing agent. The sum of the percentages of the components is 100 percent. The invention has the advantages that when UV coating is carried out in some cabinets and drawers, the problem of strong pungent smell remained in a paint film after the traditional ultraviolet roller coating matt varnish is cured for a long time can be solved. However, the technical problems of poor scratch resistance and scratch resistance of the matte varnish cannot be solved in the prior art.
In summary, how to improve scratch resistance of the matte varnish has become a technical problem to be solved in the industry.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide high-permeability scratch-resistant automobile matte varnish and a preparation method thereof. The high-permeability scratch-resistant automobile matte varnish provided by the invention has the advantages that the film hardness is high, the surface of the film has more excellent scratch resistance or other defect generation resistance, the surface scratch resistance is high, the film is not easy to scratch and damage, better protection can be provided, the wear resistance is excellent, the permeability is higher, and the surface of the film has smooth hand feeling.
The technical scheme of the invention is as follows:
the high-permeability scratch-resistant automobile matte varnish comprises the following components in percentage by mass:
10-15% of butyl acetate, 5-10% of propylene glycol methyl ether acetate, 5-6% of cyclohexanone, 4-5% of dispersing agent, 40-63.2% of acrylic resin, 8-12% of matte powder (matting powder), 3-6% of PMMA (polymethyl methacrylate) powder, 0.1-1.0% of leveling agent, 0.1-1.0% of fumed silica, 0.5-1.0% of ultraviolet absorbent, 1-2% of scratch-resistant wear-resistant agent and 0.1-1.0% of organosilicon surface slipping auxiliary agent.
Further, the high-permeability scratch-resistant automobile matt varnish comprises the following components in percentage by mass: 12.5% of butyl acetate, 8.6% of propylene glycol methyl ether acetate, 5% of cyclohexanone, 5% of dispersing agent, 50% of acrylic resin, 10% of matte powder, 5% of PMMA powder, 0.5% of flatting agent, 0.5% of fumed silica, 1.0% of ultraviolet absorbent, 1.4% of scratch-resistant and wear-resistant agent and 0.5% of organosilicon surface slipping auxiliary agent.
Further, the leveling agent is BYK-358N leveling agent.
Further, the scratch-resistant wear-resistant agent comprises the following components in parts by weight: 15-25 parts of nano-composite, 3-4 parts of coupling agent, 1-2 parts of polyethylene glycol-40 hydrogenated castor oil and 7-9 parts of hydroxypropyl methyl cellulose.
Further, the scratch-resistant wear-resistant agent comprises the following components in parts by weight: 18 parts of nano-composite, 3.5 parts of coupling agent, 1.3 parts of polyethylene glycol-40 hydrogenated castor oil and 8 parts of hydroxypropyl methyl cellulose.
Further, the nanocomposite includes nano aluminum oxide, nano silicon nitride, and nano zinc powder.
Further, the mass ratio of the nano aluminum oxide, the nano silicon nitride and the nano zinc powder in the nano composite is 8-11:4-6:1-2.
Further, the coupling agent is one or more of vinyl trimethoxy silane, 3-aminopropyl triethoxy silane and gamma-methacryloxypropyl trimethoxy silane.
The invention also provides a preparation method of the high-permeability scratch-resistant automobile matte varnish, which comprises the following steps:
s1, adding formula amounts of butyl acetate, propylene glycol methyl ether acetate and cyclohexanone, and stirring at a stirring speed of 200-300r/min;
s2, adding a dispersing agent into the step S1 while stirring, wherein the stirring speed is 200-300r/min, and the stirring time is 3-5min;
s3, adding the formula amount of acrylic resin into the step S2, and stirring at the stirring speed of 200-300r/min for 3-5min;
s4, adding the matte powder, the fumed silica, the PMMA powder and the scratch-resistant wear-resistant agent in the formula amount into the step S3, and stirring at the stirring speed of 700-900r/min for 25-35min to obtain a material A;
s5, grinding the material A obtained in the step S4 by a sand mill, wherein the rotation speed of the sand mill is 1200-1400r/min, and circularly grinding for 0.5h until the fineness is less than or equal to 20 mu m to obtain a material B;
and S6, adding the leveling agent, the ultraviolet absorber and the organosilicon surface slipping auxiliary agent with the formula amount into the material B obtained in the step S5 while stirring, and uniformly stirring to obtain the modified silicone adhesive.
Scratch and mar of paint surfaces using the matte varnish are difficult to repair, and forced repair may eventually lead to an inconsistent paint surface appearance. Therefore, how to improve the scratch resistance of the matt varnish becomes a great difficulty for automobile coatings. The present invention has attempted to incorporate existing commercial abrasion and scratch resistant agents into matte varnish formulations, but with undesirable results. The scratch-resistant wear-resistant agent with good effect is obtained through a large number of creative experiments. The scratch-resistant antiwear agent provided by the invention is prepared from a nano-composite, a coupling agent, polyethylene glycol-40 hydrogenated castor oil, hydroxypropyl methylcellulose and the like. According to the invention, the nano-composite is treated by the coupling agent and the polyethylene glycol-40 hydrogenated castor oil, so that the coupling agent and the polyethylene glycol-40 hydrogenated castor oil can be uniformly coated on the surface of the nano-composite, the nano particles can be well dispersed, the effect of the nano particles can be exerted, the addition of the hydroxypropyl methylcellulose can greatly improve the compatibility between the nano particles and each component in a matte varnish system, the synergistic effect between the nano particles and each component in the matte varnish system can be exerted, the nano particles are tightly combined on the surface of a substrate in the process of forming a paint film by the paint, and the scratch resistance, scratch resistance and wear resistance of the paint film can be remarkably improved on the premise that the permeability of the paint film is not changed, meanwhile, the exposure aging time of the paint film can be prolonged, and the weather resistance of the paint film is improved.
Compared with the prior art, the invention has the following advantages:
(1) The high-permeability scratch-resistant automobile matte varnish provided by the invention has the advantages that the paint film is high in hardness, the surface of the paint film has more excellent scratch resistance or other defect generation resistance, the scratch resistance of the surface is high, the paint film is not easy to scratch and damage, better protection can be provided, and the wear resistance is excellent.
(2) The matte powder particle size selected by the invention is relatively thin (the average particle size is 1.5 mu m), and the permeability of a matte varnish film can be improved by adding grinding dispersion, and the surface of the film is fine and soft.
(3) The high-permeability scratch-resistant automobile matte varnish provided by the invention can effectively prolong the exposure aging time of a paint film and has excellent weather resistance.
Detailed Description
The invention is further illustrated by the following description of specific embodiments, which are not intended to be limiting, and various modifications or improvements can be made by those skilled in the art in light of the basic idea of the invention, but are within the scope of the invention without departing from the basic idea of the invention.
The raw materials used in the invention are all commercially available unless otherwise specified. The information on the manufacturer of each raw material in the following examples and comparative examples is shown in table 1.
Table 1: information of purchasing manufacturer of each raw material
Example 1, high-permeability scratch-resistant automotive matt varnish
The high-permeability scratch-resistant automobile matte varnish comprises the following components in percentage by mass:
10% of butyl acetate, 5% of propylene glycol methyl ether acetate, 5% of cyclohexanone, 4% of dispersing agent, 63.2% of acrylic resin, 8% of matte powder, 3% of PMMA powder, 0.1% of flatting agent, 0.1% of fumed silica, 0.5% of ultraviolet absorbent, 1% of scratch-resistant and wear-resistant agent and 0.1% of organosilicon surface slipping auxiliary agent; the dispersing agent is BYK-2009; the leveling agent is BYK-358N leveling agent; the ultraviolet absorber comprises an ultraviolet absorber UV-328 and an ultraviolet absorber UV-531 according to a mass ratio of 3:2, composing; the organosilicon surface slipping auxiliary agent is BYK-333.
The scratch-resistant wear-resistant agent comprises the following components in parts by weight: 15 parts of nano-composite, 3 parts of coupling agent, 1 part of polyethylene glycol-40 hydrogenated castor oil and 7 parts of hydroxypropyl methyl cellulose; the nano composite comprises nano aluminum oxide, nano silicon nitride and nano zinc powder; the mass ratio of the nano aluminum oxide, the nano silicon nitride and the nano zinc powder in the nano composite is 8:6:2; the coupling agent is vinyl trimethoxy silane.
The preparation method of the scratch-resistant antiwear agent comprises the following steps:
(1) Drying the nanocomposite at 105 ℃ for 8 hours, adding absolute ethyl alcohol into the dried nanocomposite, wherein the mass of the absolute ethyl alcohol is 10 times of that of the dried nanocomposite, and soaking for 12 hours to obtain a nanocomposite material;
(2) Mixing a coupling agent and polyethylene glycol-40 hydrogenated castor oil, adding absolute ethyl alcohol, wherein the addition amount of the absolute ethyl alcohol is 30 times of the total mass of the coupling agent and the polyethylene glycol-40 hydrogenated castor oil, and uniformly stirring to obtain a mixed solution;
(3) Adding the nanocomposite obtained in the step (1) into the mixed solution obtained in the step (2), uniformly stirring, performing ultrasonic dispersion for 8min, placing in a constant-temperature water bath at 70 ℃ for stirring for 25min, filtering, drying a filter cake obtained after filtering, and grinding to obtain a mixed material;
(4) Taking hydroxypropyl methylcellulose, adding water, wherein the adding amount of water is 42 times of the mass of the hydroxypropyl methylcellulose, fully stirring, adding the mixed material obtained in the step (3), performing ultrasonic dispersion at 70 ℃ for 15min, filtering, drying a filter cake obtained after filtering, and grinding to obtain the hydroxypropyl methylcellulose.
The preparation method of the high-permeability scratch-resistant automobile matte varnish comprises the following steps of:
s1, adding formula amounts of butyl acetate, propylene glycol methyl ether acetate and cyclohexanone, and stirring at a stirring speed of 200r/min;
s2, adding a dispersing agent into the step S1 while stirring, wherein the stirring speed is 200r/min, and the stirring time is 3min;
s3, adding the formula amount of acrylic resin into the step S2, and stirring at the stirring speed of 200r/min for 3min;
s4, adding the matte powder, the fumed silica, the PMMA powder and the scratch-resistant wear-resistant agent according to the formula amount into the step S3, and stirring at the stirring speed of 700r/min for 25min to obtain a material A;
s5, grinding the material A obtained in the step S4 by a sand mill, wherein the rotation speed of the sand mill is 1200r/min, and circularly grinding for 0.5h until the fineness is less than or equal to 20 mu m, so as to obtain a material B;
and S6, adding the leveling agent, the ultraviolet absorber and the organosilicon surface slipping auxiliary agent with the formula amount into the material B obtained in the step S5 while stirring, and uniformly stirring to obtain the modified silicone adhesive.
Example 2, high-permeability scratch-resistant automotive matt varnish
The high-permeability scratch-resistant automobile matte varnish comprises the following components in percentage by mass:
15% of butyl acetate, 10% of propylene glycol methyl ether acetate, 6% of cyclohexanone, 5% of dispersing agent, 40% of acrylic resin, 12% of matte powder, 6% of PMMA powder, 1.0% of flatting agent, 1.0% of fumed silica, 1.0% of ultraviolet absorbent, 2% of scratch-resistant and wear-resistant agent and 1.0% of organosilicon surface slipping auxiliary agent; the dispersing agent is BYK-2009; the leveling agent is BYK-358N leveling agent; the ultraviolet absorber comprises an ultraviolet absorber UV-328 and an ultraviolet absorber UV-531 according to a mass ratio of 6:1, the composition is as follows; the organosilicon surface slipping auxiliary agent is BYK-333;
the scratch-resistant wear-resistant agent comprises the following components in parts by weight: 25 parts of nano-composite, 4 parts of coupling agent, 2 parts of polyethylene glycol-40 hydrogenated castor oil and 9 parts of hydroxypropyl methyl cellulose; the nano composite comprises nano aluminum oxide, nano silicon nitride and nano zinc powder; the mass ratio of the nano aluminum oxide, the nano silicon nitride and the nano zinc powder in the nano composite is 11:4:1, a step of; the coupling agent is prepared from vinyl trimethoxy silane and 3-aminopropyl triethoxy silane according to the mass ratio of 1: 3.
The preparation method of the scratch-resistant antiwear agent comprises the following steps:
(1) Drying the nanocomposite at 115 ℃ for 12 hours, adding absolute ethyl alcohol into the dried nanocomposite, wherein the mass of the absolute ethyl alcohol is 15 times that of the dried nanocomposite, and soaking for 16 hours to obtain a nanocomposite;
(2) Mixing a coupling agent and polyethylene glycol-40 hydrogenated castor oil, adding absolute ethyl alcohol, wherein the addition amount of the absolute ethyl alcohol is 40 times of the total mass of the coupling agent and the polyethylene glycol-40 hydrogenated castor oil, and uniformly stirring to obtain a mixed solution;
(3) Adding the nanocomposite obtained in the step (1) into the mixed solution obtained in the step (2), uniformly stirring, performing ultrasonic dispersion for 13min, placing in a constant-temperature water bath at 80 ℃ for stirring for 35min, filtering, drying a filter cake obtained after filtering, and grinding to obtain a mixed material;
(4) Taking hydroxypropyl methylcellulose, adding water with the addition amount of 48 times of the mass of the hydroxypropyl methylcellulose, fully stirring, adding the mixed material obtained in the step (3), performing ultrasonic dispersion at 80 ℃ for 25min, filtering, drying a filter cake obtained after filtering, and grinding to obtain the hydroxypropyl methylcellulose.
The preparation method of the high-permeability scratch-resistant automobile matte varnish comprises the following steps of:
s1, adding formula amounts of butyl acetate, propylene glycol methyl ether acetate and cyclohexanone, and stirring at a stirring speed of 300r/min;
s2, adding a dispersing agent into the step S1 while stirring, wherein the stirring speed is 300r/min, and the stirring time is 5min;
s3, adding the formula amount of acrylic resin into the step S2, and stirring at a stirring speed of 300r/min for 5min;
s4, adding the matte powder, the fumed silica, the PMMA powder and the scratch-resistant wear-resistant agent according to the formula amount into the step S3, and stirring at the stirring speed of 900r/min for 35min to obtain a material A;
s5, grinding the material A obtained in the step S4 by a sand mill, wherein the rotating speed of the sand mill is 1400r/min, and circularly grinding for 0.5h until the fineness is less than or equal to 20 mu m to obtain a material B;
and S6, adding the leveling agent, the ultraviolet absorber and the organosilicon surface slipping auxiliary agent with the formula amount into the material B obtained in the step S5 while stirring, and uniformly stirring to obtain the modified silicone adhesive.
Example 3, high-permeability scratch-resistant automotive matt varnish
The high-permeability scratch-resistant automobile matte varnish comprises the following components in percentage by mass:
12.5% of butyl acetate, 8.6% of propylene glycol methyl ether acetate, 5% of cyclohexanone, 5% of dispersing agent, 50% of acrylic resin, 10% of matte powder, 5% of PMMA powder, 0.5% of flatting agent, 0.5% of fumed silica, 1.0% of ultraviolet absorbent, 1.4% of scratch-resistant and wear-resistant agent and 0.5% of organosilicon surface slipping auxiliary agent; the dispersing agent is BYK-2009; the leveling agent is BYK-358N leveling agent; the ultraviolet absorber comprises an ultraviolet absorber UV-328 and an ultraviolet absorber UV-531 according to a mass ratio of 5:2, composing; the organosilicon surface slipping auxiliary agent is BYK-333;
the scratch-resistant wear-resistant agent comprises the following components in parts by weight: 18 parts of nano-composite, 3.5 parts of coupling agent, 1.3 parts of polyethylene glycol-40 hydrogenated castor oil and 8 parts of hydroxypropyl methyl cellulose; the nano composite comprises nano aluminum oxide, nano silicon nitride and nano zinc powder; the mass ratio of the nano aluminum oxide, the nano silicon nitride and the nano zinc powder in the nano composite is 9:5:1, a step of; the coupling agent is prepared from 3-aminopropyl triethoxysilane and gamma-methacryloxypropyl trimethoxysilane according to the mass ratio of 1: 4.
The preparation method of the scratch-resistant antiwear agent comprises the following steps:
(1) Drying the nanocomposite at 110 ℃ for 10 hours, adding absolute ethyl alcohol into the dried nanocomposite, wherein the mass of the absolute ethyl alcohol is 14 times that of the dried nanocomposite, and soaking for 15 hours to obtain a nanocomposite;
(2) Mixing a coupling agent and polyethylene glycol-40 hydrogenated castor oil, adding absolute ethyl alcohol, wherein the addition amount of the absolute ethyl alcohol is 36 times of the total mass of the coupling agent and the polyethylene glycol-40 hydrogenated castor oil, and uniformly stirring to obtain a mixed solution;
(3) Adding the nanocomposite obtained in the step (1) into the mixed solution obtained in the step (2), uniformly stirring, performing ultrasonic dispersion for 11min, placing in a constant-temperature water bath at 76 ℃ for stirring for 32min, filtering, drying a filter cake obtained after filtering, and grinding to obtain a mixed material;
(4) Taking hydroxypropyl methylcellulose, adding water, the adding amount of the water is 45 times of the mass of the hydroxypropyl methylcellulose, fully stirring, adding the mixed material obtained in the step (3), carrying out ultrasonic dispersion at 78 ℃ for 17min, filtering, drying a filter cake obtained after filtering, and grinding to obtain the hydroxypropyl methylcellulose.
The preparation method of the high-permeability scratch-resistant automobile matte varnish comprises the following steps of:
s1, adding formula amounts of butyl acetate, propylene glycol methyl ether acetate and cyclohexanone, and stirring at a stirring speed of 240r/min;
s2, adding a dispersing agent into the step S1 while stirring, wherein the stirring speed is 240r/min, and the stirring time is 4min;
s3, adding the formula amount of acrylic resin into the step S2, and stirring at a stirring speed of 260r/min for 5min;
s4, adding the matte powder, the fumed silica, the PMMA powder and the scratch-resistant wear-resistant agent in the formula amount into the step S3, and stirring at the stirring speed of 800r/min for 32min to obtain a material A;
s5, grinding the material A obtained in the step S4 by a sand mill, wherein the rotating speed of the sand mill is 1300r/min, and the grinding is circularly carried out for 0.5h until the fineness is less than or equal to 20 mu m, so as to obtain a material B;
and S6, adding the leveling agent, the ultraviolet absorber and the organosilicon surface slipping auxiliary agent with the formula amount into the material B obtained in the step S5 while stirring, and uniformly stirring to obtain the modified silicone adhesive.
Comparative example 1, automotive matt varnish
The automobile matt varnish comprises the following components in percentage by mass:
12.5% of butyl acetate, 8.6% of propylene glycol methyl ether acetate, 5% of cyclohexanone, 5% of dispersing agent, 50% of acrylic resin, 10% of matte powder, 5% of PMMA powder, 0.5% of flatting agent, 0.5% of fumed silica, 1.0% of ultraviolet absorbent, 1.4% of scratch-resistant and wear-resistant agent and 0.5% of organosilicon surface slipping auxiliary agent; the dispersing agent is BYK-2009; the leveling agent is BYK-358N leveling agent; the ultraviolet absorber comprises an ultraviolet absorber UV-328 and an ultraviolet absorber UV-531 according to a mass ratio of 5:2, composing; the organosilicon surface slipping auxiliary agent is BYK-333;
the scratch-resistant wear-resistant agent comprises the following components in parts by weight: 18 parts of nano-composite, 3.5 parts of coupling agent, 1.3 parts of polyethylene glycol-40 hydrogenated castor oil and 8 parts of hydroxypropyl methyl cellulose; the nano composite comprises nano aluminum oxide, nano silicon nitride and nano zinc powder; the mass ratio of the nano aluminum oxide, the nano silicon nitride and the nano zinc powder in the nano composite is 1:1:1, a step of; the coupling agent is prepared from 3-aminopropyl triethoxysilane and gamma-methacryloxypropyl trimethoxysilane according to the mass ratio of 1: 4.
The preparation methods of the scratch-resistant antiwear agent and the automobile matte varnish are similar to those of the example 3;
the difference from example 3 is that the mass ratio of nano alumina, nano silicon nitride and nano zinc powder in the nano composite is 1:1:1.
comparative example 2, automotive matt varnish
The automobile matt varnish comprises the following components in percentage by mass:
12.5% of butyl acetate, 8.6% of propylene glycol methyl ether acetate, 5% of cyclohexanone, 5% of dispersing agent, 50% of acrylic resin, 10% of matte powder, 5% of PMMA powder, 0.5% of flatting agent, 0.5% of fumed silica, 1.0% of ultraviolet absorbent, 1.4% of scratch-resistant and wear-resistant agent and 0.5% of organosilicon surface slipping auxiliary agent; the dispersing agent is BYK-2009; the leveling agent is BYK-358N leveling agent; the ultraviolet absorber comprises an ultraviolet absorber UV-328 and an ultraviolet absorber UV-531 according to a mass ratio of 5:2, composing; the organosilicon surface slipping auxiliary agent is BYK-333;
the scratch-resistant wear-resistant agent comprises the following components in parts by weight: 18 parts of nano-composite, 3.5 parts of coupling agent, 1.3 parts of polyethylene glycol-40 hydrogenated castor oil and 8 parts of hydroxypropyl methyl cellulose; the nanocomposite comprises nano aluminum oxide and nano silicon nitride; the mass ratio of the nano aluminum oxide to the nano silicon nitride in the nano composite is 9:5, a step of; the coupling agent is prepared from 3-aminopropyl triethoxysilane and gamma-methacryloxypropyl trimethoxysilane according to the mass ratio of 1: 4.
The preparation methods of the scratch-resistant antiwear agent and the automobile matte varnish are similar to those of the example 3;
the difference from example 3 is that the nanocomposite was free of added nano zinc powder.
Comparative example 3, automotive matt varnish
The automobile matt varnish comprises the following components in percentage by mass:
12.5% of butyl acetate, 8.6% of propylene glycol methyl ether acetate, 5% of cyclohexanone, 5% of dispersing agent, 50% of acrylic resin, 10% of matte powder, 5% of PMMA powder, 0.5% of flatting agent, 0.5% of fumed silica, 1.0% of ultraviolet absorbent, 1.4% of scratch-resistant and wear-resistant agent and 0.5% of organosilicon surface slipping auxiliary agent; the dispersing agent is BYK-2009; the leveling agent is BYK-358N leveling agent; the ultraviolet absorber comprises an ultraviolet absorber UV-328 and an ultraviolet absorber UV-531 according to a mass ratio of 5:2, composing; the organosilicon surface slipping auxiliary agent is BYK-333;
the scratch-resistant wear-resistant agent comprises the following components in parts by weight: 18 parts of nano-composite, 3.5 parts of coupling agent, 1.3 parts of hydrogenated castor oil and 8 parts of hydroxypropyl methyl cellulose; the nano composite comprises nano aluminum oxide, nano silicon nitride and nano zinc powder; the mass ratio of the nano aluminum oxide, the nano silicon nitride and the nano zinc powder in the nano composite is 9:5:1, a step of; the coupling agent is prepared from 3-aminopropyl triethoxysilane and gamma-methacryloxypropyl trimethoxysilane according to the mass ratio of 1: 4.
The preparation methods of the scratch-resistant antiwear agent and the automobile matte varnish are similar to those of the example 3;
the difference from example 3 is that the polyethylene glycol-40 hydrogenated castor oil in the scratch-resistant antiwear agent is replaced by hydrogenated castor oil.
Comparative example 4, automotive matt varnish
The automobile matt varnish comprises the following components in percentage by mass:
12.5% of butyl acetate, 8.6% of propylene glycol methyl ether acetate, 5% of cyclohexanone, 5% of dispersing agent, 50% of acrylic resin, 10% of matte powder, 5% of PMMA powder, 0.5% of flatting agent, 0.5% of fumed silica, 1.0% of ultraviolet absorbent, 1.4% of scratch-resistant and wear-resistant agent and 0.5% of organosilicon surface slipping auxiliary agent; the dispersing agent is BYK-2009; the leveling agent is BYK-358N leveling agent; the ultraviolet absorber comprises an ultraviolet absorber UV-328 and an ultraviolet absorber UV-531 according to a mass ratio of 5:2, composing; the organosilicon surface slipping auxiliary agent is BYK-333;
the scratch-resistant wear-resistant agent comprises the following components in parts by weight: 18 parts of nano-composite, 3.5 parts of coupling agent and 8 parts of hydroxypropyl methyl cellulose; the nano composite comprises nano aluminum oxide, nano silicon nitride and nano zinc powder; the mass ratio of the nano aluminum oxide, the nano silicon nitride and the nano zinc powder in the nano composite is 9:5:1, a step of; the coupling agent is prepared from 3-aminopropyl triethoxysilane and gamma-methacryloxypropyl trimethoxysilane according to the mass ratio of 1: 4.
The preparation methods of the scratch-resistant antiwear agent and the automobile matte varnish are similar to those of the example 3;
the difference from example 3 is that no polyethylene glycol-40 hydrogenated castor oil was added to the scratch-resistant antiwear agent.
Comparative example 5, automotive matt varnish
The automobile matt varnish comprises the following components in percentage by mass:
12.5% of butyl acetate, 8.6% of propylene glycol methyl ether acetate, 5% of cyclohexanone, 5% of dispersing agent, 50% of acrylic resin, 10% of matte powder, 5% of PMMA powder, 0.5% of flatting agent, 0.5% of fumed silica, 1.0% of ultraviolet absorbent, 1.4% of scratch-resistant and wear-resistant agent and 0.5% of organosilicon surface slipping auxiliary agent; the dispersing agent is BYK-2009; the leveling agent is BYK-358N leveling agent; the ultraviolet absorber comprises an ultraviolet absorber UV-328 and an ultraviolet absorber UV-531 according to a mass ratio of 5:2, composing; the organosilicon surface slipping auxiliary agent is BYK-333;
the scratch-resistant wear-resistant agent comprises the following components in parts by weight: 18 parts of nano-composite, 3.5 parts of coupling agent, 1.3 parts of polyethylene glycol-40 hydrogenated castor oil and 8 parts of carboxymethyl cellulose; the nano composite comprises nano aluminum oxide, nano silicon nitride and nano zinc powder; the mass ratio of the nano aluminum oxide, the nano silicon nitride and the nano zinc powder in the nano composite is 9:5:1, a step of; the coupling agent is prepared from 3-aminopropyl triethoxysilane and gamma-methacryloxypropyl trimethoxysilane according to the mass ratio of 1: 4.
The preparation methods of the scratch-resistant antiwear agent and the automobile matte varnish are similar to those of the example 3;
the difference from example 3 is that hydroxypropyl methylcellulose in the scratch-resistant antiwear agent is replaced by carboxymethyl cellulose.
Comparative example 6, automotive matt varnish
The automobile matt varnish comprises the following components in percentage by mass:
12.5% of butyl acetate, 8.6% of propylene glycol methyl ether acetate, 5% of cyclohexanone, 5% of dispersing agent, 50% of acrylic resin, 10% of matte powder, 5% of PMMA powder, 0.5% of flatting agent, 0.5% of fumed silica, 1.0% of ultraviolet absorbent, 1.4% of scratch-resistant and wear-resistant agent and 0.5% of organosilicon surface slipping auxiliary agent; the dispersing agent is BYK-2009; the leveling agent is BYK-358N leveling agent; the ultraviolet absorber comprises an ultraviolet absorber UV-234 and an ultraviolet absorber UV-531 according to a mass ratio of 5:2, composing; the organosilicon surface slipping auxiliary agent is BYK-333;
the scratch-resistant wear-resistant agent comprises the following components in parts by weight: 18 parts of nano-composite, 3.5 parts of coupling agent, 1.3 parts of polyethylene glycol-40 hydrogenated castor oil and 8 parts of hydroxypropyl methyl cellulose; the nano composite comprises nano aluminum oxide, nano silicon nitride and nano zinc powder; the mass ratio of the nano aluminum oxide, the nano silicon nitride and the nano zinc powder in the nano composite is 9:5:1, a step of; the coupling agent is prepared from 3-aminopropyl triethoxysilane and gamma-methacryloxypropyl trimethoxysilane according to the mass ratio of 1: 4.
The preparation methods of the scratch-resistant antiwear agent and the automobile matte varnish are similar to those of the example 3;
the difference from example 3 is that the ultraviolet absorber is composed of an ultraviolet absorber UV-234 and an ultraviolet absorber UV-531 in a mass ratio of 5: 2.
Test example one, film permeability and hand smoothness test
1. Test materials: the high-permeability scratch-resistant automobile matt varnish prepared in example 1, example 2 and example 3.
2. The test method comprises the following steps:
the same substrate was prepared, and after drying, the same black base paint was sprayed on the substrate, and after drying, the high-permeability scratch-resistant automotive matt varnish prepared in example 1, example 2 and example 3 was sprayed, and after drying, the permeability of the comparative color was visually examined, and the smoothness was felt by hand. The permeability of the paint film and the smoothness of the hand feeling of the paint film are respectively 0-9 min, 0 min and 9 min.
3. Test results: the test results are shown in Table 2.
Table 2: results of film penetration and hand smoothness test
| Detecting items | Example 1 | Example 2 | Example 3 |
| Film permeability | 6 | 8 | 9 |
| Smooth hand feeling of paint film | 7 | 8 | 8 |
As can be seen from Table 2, the high-permeability scratch-resistant automobile matt varnish prepared in examples 1-3 of the invention has higher permeability of the varnish film and smooth hand feeling on the surface of the varnish film. The high-permeability scratch-resistant automobile matt varnish prepared in the embodiment 3 of the invention has a paint film permeability score of 9 minutes, a paint film hand feeling smoothness score of 8 minutes, and the paint film permeability and the paint film hand feeling smoothness are optimal, so that the high-permeability scratch-resistant automobile matt varnish is the best embodiment of the invention.
Test example two, paint film abrasion resistance test
1. Test materials: the high permeability scratch resistant automotive matt varnish prepared in example 3, and the automotive matt varnishes prepared in comparative examples 1, 2, 3, 4 and 5.
2. The test method comprises the following steps:
the high-permeability scratch-resistant automotive matt varnish prepared by the invention, comparative example 1, comparative example 2, comparative example 3, comparative example 4 and comparative example 5 were tested for abrasion resistance by referring to GB/T1768-2006 method for measuring abrasion resistance of colored paint and varnish by rotating rubber grinding wheel.
3. Test results: the test results are shown in Table 3.
Table 3: results of the abrasion resistance test of paint film
As can be seen from Table 3, the mass loss of the paint film of the high-permeability scratch-resistant automobile matt varnish prepared by the invention is as low as 18.1mg after the abrasion resistance experiment, which is obviously lower than that of the paint films of the automobile matt varnishes prepared by comparative examples 1, 2, 3, 4 and 5. This shows that the paint film surface of the high-permeability scratch-resistant automobile matt varnish provided by the invention has more excellent wear resistance.
Test example III, paint film hardness test
1. Test materials: the high permeability scratch resistant automotive matt varnish prepared in example 3, and the automotive matt varnishes prepared in comparative examples 1, 2, 3, 4 and 5.
2. The test method comprises the following steps:
the pencil hardness of the high-permeability scratch-resistant automotive matt varnish prepared by the invention and the automotive matt varnishes prepared by comparative examples 1, 2, 3, 4 and 5 were tested by referring to GB/T6739-2006 measurement of paint film hardness by the colored paint and varnish pencil method, so as to judge the scratch resistance of the paint film.
3. The test results are shown in Table 4.
Table 4: paint film hardness test results
| Detecting items | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| Hardness of pencil | H | B | B | F | HB | HB |
As can be seen from Table 4, the pencil hardness of the high-permeability scratch-resistant automotive matt varnish prepared by the invention can reach H, and the pencil hardness of the automotive matt varnishes prepared by comparative examples 1, 2, 3, 4 and 5 are B, B, F, HB, HB respectively. Compared with comparative examples 1, 2, 3, 4 and 5, the pencil hardness of the high-permeability scratch-resistant automotive matte varnish provided by the invention is higher. The high-permeability scratch-resistant automobile matt varnish disclosed by the invention has more excellent scratch resistance or other defect generation resistance on the surface of a paint film, so that the paint film is not easy to scratch and damage, and better protection can be provided.
Test example four, weather resistance test
1. Test materials: high-permeability scratch-resistant automobile matt varnish prepared in example 3 and automobile matt varnishes prepared in comparative examples 2 and 6.
2. The test method comprises the following steps: the manual accelerated aging test reaches the test time of light loss level 1 and color change level 1 by referring to the relevant standards of GB/T1865-2009 (Xe arc radiation filtered by artificial weathering and artificial radiation exposure of colored paint and varnish) and GB/T1766-2008 (rating method of colored paint and varnish coating aging).
3. The test results are shown in Table 5.
Table 5: weather resistance test results
| Detecting items | Example 3 | Comparative example 2 | Comparative example 6 |
| Test time | 1500h | 1400h | 1400h |
As can be seen from Table 5, the high-permeability scratch-resistant automobile matt varnish prepared by the invention reaches the test time of 1 level of light loss and 1 level of color change through the artificial accelerated aging test to be 1500 hours, and the automobile matt varnish prepared by the comparative examples 2 and 6 reaches the test time of 1 level of light loss and 1 level of color change through the artificial accelerated aging test to be 1400 hours and 1400 hours respectively. Compared with comparative examples 2 and 6, the high-permeability scratch-resistant automobile matt varnish provided by the invention has better weather resistance.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (6)
1. The high-permeability scratch-resistant automobile matte varnish is characterized by comprising the following components in percentage by mass:
10-15% of butyl acetate, 5-10% of propylene glycol methyl ether acetate, 5-6% of cyclohexanone, 4-5% of dispersing agent, 40-63.2% of acrylic resin, 8-12% of matte powder, 3-6% of PMMA powder, 0.1-1.0% of flatting agent, 0.1-1.0% of fumed silica, 0.5-1.0% of ultraviolet absorbent, 1-2% of scratch-resistant wear-resistant agent and 0.1-1.0% of organosilicon surface slipping auxiliary agent;
the scratch-resistant wear-resistant agent comprises the following components in parts by weight: 15-25 parts of nano-composite, 3-4 parts of coupling agent, 1-2 parts of polyethylene glycol-40 hydrogenated castor oil and 7-9 parts of hydroxypropyl methyl cellulose;
the nano composite comprises nano aluminum oxide, nano silicon nitride and nano zinc powder;
the mass ratio of the nano aluminum oxide, the nano silicon nitride and the nano zinc powder in the nano composite is 8-11:4-6:1-2.
2. The high-permeability scratch-resistant automotive matt varnish according to claim 1, comprising the following components in percentage by mass: 12.5% of butyl acetate, 8.6% of propylene glycol methyl ether acetate, 5% of cyclohexanone, 5% of dispersing agent, 50% of acrylic resin, 10% of matte powder, 5% of PMMA powder, 0.5% of flatting agent, 0.5% of fumed silica, 1.0% of ultraviolet absorbent, 1.4% of scratch-resistant and wear-resistant agent and 0.5% of organosilicon surface slipping auxiliary agent.
3. The high-permeability scratch-resistant automotive matt varnish according to claim 1 or 2, characterized in that the levelling agent is a BYK-358N levelling agent.
4. The high-permeability scratch-resistant automobile matt varnish according to claim 1, wherein the scratch-resistant wear-resistant agent comprises the following components in parts by weight: 18 parts of nano-composite, 3.5 parts of coupling agent, 1.3 parts of polyethylene glycol-40 hydrogenated castor oil and 8 parts of hydroxypropyl methyl cellulose.
5. The high permeability scratch resistant automotive matt varnish, according to claim 1, wherein the coupling agent is one or more of vinyl trimethoxysilane, 3-aminopropyl triethoxysilane, gamma-methacryloxypropyl trimethoxysilane.
6. The method for preparing the high-permeability scratch-resistant automotive matt varnish, according to any of claims 1 to 5, comprising the steps of:
s1, adding formula amounts of butyl acetate, propylene glycol methyl ether acetate and cyclohexanone, and stirring at a stirring speed of 200-300r/min;
s2, adding a dispersing agent into the step S1 while stirring, wherein the stirring speed is 200-300r/min, and the stirring time is 3-5min;
s3, adding the formula amount of acrylic resin into the step S2, and stirring at the stirring speed of 200-300r/min for 3-5min;
s4, adding the matte powder, the fumed silica, the PMMA powder and the scratch-resistant wear-resistant agent in the formula amount into the step S3, and stirring at the stirring speed of 700-900r/min for 25-35min to obtain a material A;
s5, grinding the material A obtained in the step S4 by a sand mill, wherein the rotation speed of the sand mill is 1200-1400r/min, and circularly grinding for 0.5h until the fineness is less than or equal to 20 mu m to obtain a material B;
and S6, adding the leveling agent, the ultraviolet absorber and the organosilicon surface slipping auxiliary agent with the formula amount into the material B obtained in the step S5 while stirring, and uniformly stirring to obtain the modified silicone adhesive.
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| KR101989438B1 (en) * | 2014-09-12 | 2019-06-17 | (주)엘지하우시스 | Matte coating composition |
| CN104449223A (en) * | 2014-11-25 | 2015-03-25 | 南京航空航天大学 | Aluminum-zinc-silicon epoxy composite powder anticorrosive coating and preparation method thereof |
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| CN106675257B (en) * | 2016-12-14 | 2020-06-09 | 东来涂料技术（上海）股份有限公司 | Safe environment-friendly semi-matte varnish for automotive interior parts and preparation method thereof |
| CN113683952A (en) * | 2021-09-02 | 2021-11-23 | 湖南宏泰新材料有限公司 | Rubber hand-feeling anti-dazzle anti-fingerprint wear-resistant hardening liquid and preparation method thereof |
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