CN111515100B - Preparation method of impact-resistant glass based on chemical pretreatment - Google Patents
Preparation method of impact-resistant glass based on chemical pretreatment Download PDFInfo
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- CN111515100B CN111515100B CN202010378373.8A CN202010378373A CN111515100B CN 111515100 B CN111515100 B CN 111515100B CN 202010378373 A CN202010378373 A CN 202010378373A CN 111515100 B CN111515100 B CN 111515100B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/002—Pretreatement
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- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/007—After-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0209—Multistage baking
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
- B05D3/0272—After-treatment with ovens
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
- B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
- B05D3/065—After-treatment
- B05D3/067—Curing or cross-linking the coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/54—No clear coat specified
- B05D7/544—No clear coat specified the first layer is let to dry at least partially before applying the second layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2203/00—Other substrates
- B05D2203/30—Other inorganic substrates, e.g. ceramics, silicon
- B05D2203/35—Glass
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Abstract
The invention discloses a preparation method of impact-resistant glass based on chemical pretreatment, wherein an impact-resistant coating comprises the following components in parts by weight: 20-30 parts of condensed type silicon resin, 2-10 parts of vinyl silicon resin, 1-5 parts of curing agent, 1-5 parts of adhesion promoter, 0.1-1 part of flatting agent and 55-65 parts of solvent; the glass substrate is sprayed with the coarsening liquid in a vertical and rotary inclined mode in sequence, so that the coarsening liquid corrodes the surface of the glass substrate to form longitudinal and transverse pits, the bonding strength of the coating and the secondary coarsening glass substrate can be improved, the impact resistance of the impact-resistant glass prepared by the method is improved by over 90 percent, the coating has high hardness, is not yellow, has strong adhesiveness and washing resistance, is not easy to fall off, and has good weather resistance and durability.
Description
Technical Field
The invention relates to the technical field of impact-resistant glass, in particular to a preparation method of impact-resistant glass based on chemical pretreatment.
Background
Glass is an important material with a wide range of application markets, from construction, automotive, flat panel displays, wearable electronics, to optical instruments, and the like. In order to meet the requirements of use, the impact resistance of the glass is generally required to be improved. The glass can be tempered or materials can be added outside the glass from two aspects.
Taking mobile phone touch screen glass as an example, the current famous brand of the pioneer cogongrass is gorilla glass of corning corporation in the United states, and the method is to chemically toughen the glass so that the glass has good impact resistance. In the method for adding materials outside glass, the mobile phone film is a convenient and low-cost solution for improving the shock resistance of the touch screen glass, but has the following defects: 1) the fingerprint-resistant agent coated on the surface of the mobile phone touch screen when leaving a factory is covered, so that the fingerprint-resistant function of the touch screen is lost; 2) the sensitivity of the touch sense of the human fingers is reduced; 3) and a plurality of complicated film pasting procedures are provided, so that the extremely-caused experience of the consumer on the product is weakened. On the contrary, the solution of coating the transparent impact-resistant coating on the back surface of the mobile phone touch screen glass can not only not weaken the extremely-caused experience of consumers on the product, but also obviously improve the impact resistance of the touch screen glass and reduce the cost.
Chinese patent CN108504184A discloses an impact-resistant ink for glass and a use method thereof, wherein the impact-resistant ink comprises the following raw materials: the printing ink comprises a photoinitiator, organic silicon modified acrylate, a vinyl coupling agent, an epoxy coupling agent, silanol resin, tetrafunctional polyurethane acrylate and a solvent, and not only improves the impact resistance of glass, but also is simple and convenient to use, and is beneficial to popularization and implementation; however, the glass impact-resistant ink has limited impact resistance and soft hardness, and a coating is easy to scratch and yellow and is not beneficial to the industrialization of products; in addition, after the existing coating is sprayed on a glass substrate, the adhesion between the coating and the glass substrate is poor, the coating is easy to bubble, deform and even fall off, and the weather resistance and the durability are poor.
Disclosure of Invention
The invention aims to provide a preparation method of impact-resistant glass based on chemical pretreatment, which adopts a sprayer to spray a glass substrate in a vertical and rotary inclined manner in sequence, so that roughening liquid corrodes the surface of the glass substrate to form longitudinal and transverse pits, and the bonding strength between a coating and a secondary roughened glass substrate can be improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of impact-resistant glass based on chemical pretreatment comprises the following steps:
s1, dissolving 20-30 parts by weight of condensed type silicone resin into 28-32 parts by weight of solvent, and magnetically stirring for 0.5-1.5 hours until the condensed type silicone resin is completely dissolved in the solvent; then 2-10 parts of vinyl silicone resin, 1-5 parts of adhesion promoter, 0.1-1 part of flatting agent and 28-32 parts of solvent are added in sequence, and magnetic stirring is carried out for 1.5-2.5 hours; after stirring, adding 1-5 parts of curing agent, and magnetically stirring for 0.2-0.8 hour to obtain the impact-resistant coating;
s2, sequentially cleaning and drying the surface of the glass substrate; taking out the dried glass substrate, vertically spraying the roughening solution on the surface of the glass substrate by using a sprayer until the surface of the glass substrate is uniformly dispersed with the water-drop roughening solution, standing the glass substrate in an environment of 35-55 ℃ for 0.5-2.5 hours, and washing and airing to obtain a primary roughened glass substrate with longitudinal pits;
s3, taking out the primarily roughened glass substrate, spraying the roughening solution on the primarily roughened glass substrate in a rotary inclined manner by a sprayer until the surface of the primarily roughened glass substrate and the side walls of the longitudinal pits are scattered with water drop-shaped roughening solution, placing the primarily roughened glass substrate with the roughening solution scattered in the primarily roughened glass substrate in an environment with the temperature of 35-55 ℃ for standing treatment for 0.5-2.5 hours, and washing and airing to obtain a secondary roughened glass substrate with longitudinal pits and transverse pits;
s4, taking out the secondary roughened glass substrate, and uniformly spraying the impact-resistant coating prepared in the step S1 on the surface of the secondary roughened glass substrate by using an automatic air spray gun, wherein the thickness of the coating is 8-12 microns;
s5, placing the glass sprayed with the impact-resistant coating in the step S4 into a baking oven at 75-85 ℃ for pre-baking for 5-10 minutes; the pre-baked glass is put into an ultraviolet UV furnace for curing, and the ultraviolet energy is controlled at 500-700mJ/cm 2 (ii) a And then placing the glass into an oven with the temperature of 165-195 ℃, curing for 30-50 minutes, and cooling to room temperature step by step to obtain the impact-resistant glass.
Preferably, the roughening solution in steps S2 and S3 is prepared from sulfuric acid and hydrofluoric acid in a ratio of 1: 2-5.
Preferably, the specific method for sequentially cleaning and drying the surface of the glass substrate in step S2 is as follows: placing the glass substrate in an ultrasonic cleaner, ultrasonically shaking in 5wt% ethanol solution at 55 ℃ for 15min, then flushing with clear water until no foam is generated, then alternately cleaning with deionized water and absolute ethyl alcohol for three times, and finally blowing with nitrogen.
Preferably, the specific method of stepwise cooling to room temperature in step S5 is as follows: putting the glass solidified at the temperature of 165-195 ℃ into the environment of 95-105 ℃, cooling for 10-35 minutes, putting the glass into the environment of 55-65 ℃, cooling for 8-32 minutes, and finally taking out the glass and naturally cooling to the room temperature.
Preferably, the condensed type silicone resin is one of T-type methyl silicone resin, D-type methyl silicone resin, T-type phenyl silicone resin, D-type phenyl silicone resin and D-type methyl phenyl silicone resin or a mixture of two or more of the T-type methyl silicone resin, the D-type methyl phenyl silicone resin and the D-type methyl phenyl silicone resin.
Preferably, the vinyl silicone resin is one or a mixture of two or more of methyl vinyl silicone resin, methyl phenyl vinyl silicone resin and methyl trifluoro propyl vinyl fluorosilicone resin.
Preferably, the curing agent is one or a mixture of more than two of benzophenone, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, ethyl orthosilicate, dibutyltin dilaurate and n-butyl borate.
Preferably, the adhesion promoter is one of gamma-aminopropyltriethoxysilane, gamma- (methacryloyloxy) -propyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane and gamma-mercaptopropyltrimethoxysilane or a mixture of more than two of the gamma-aminopropyltriethoxysilane, the gamma- (methacryloyloxy) -propyltrimethoxysilane and the gamma-mercaptopropyltrimethoxysilane.
Preferably, the leveling agent is one or a mixture of two or more of polyether modified organic silicon, polyester modified organic silicon, polydimethylsiloxane, fluorine modified acrylate and acrylate copolymer.
Preferably, the solvent is one or a mixture of more than two of ethyl acetate, butyl acetate, isopropanol, n-butanol, ethanol, ethylene glycol monobutyl ether and propylene glycol methyl ether.
After the technical scheme is adopted, compared with the background technology, the invention has the following beneficial effects:
1. the invention relates to an organic silicon system, which adopts two main materials of molecular structure highly cross-linked branched organic silicon resin (condensed type silicon resin) and silicon rubber (vinyl silicon resin) to prepare a transparent impact-resistant coating, and an interpenetrating space three-dimensional network structure can be formed between the two main materials. Highly branched silicone resins, which firstly have a very strong hardness; secondly, because the space of the molecular structure has structural defects and a large number of 'holes' exist at the branch points, when the system is impacted, the 'holes' can absorb a large amount of energy instantly, and the self deformation has a buffer effect on the generation and expansion of cracks, thereby improving the toughness of the system. On the other hand, since the silicone rubber is a linear elastic polymer material having a very low degree of crosslinking, it can further absorb external impact energy by its elastic deformation. When the external force is cancelled, the system returns to the original state, so that the system is kept intact, and the impact resistance effect is achieved. Under the synergistic effect of the two materials of the highly branched organic silicon resin and the silicon rubber, the toughness and the elasticity of the system are obviously improved, so that the glass has strong shock resistance and higher hardness.
2. In the roughening treatment process, a sprayer is adopted to vertically spray roughening liquid on the surface of a glass substrate so as to uniformly disperse drop-shaped roughening liquid on the surface of the glass substrate, and in the standing treatment process, the roughening liquid corrodes the surface of the glass substrate to obtain a primary roughened glass substrate with longitudinal pits; spraying the roughening solution on the surface of the primary roughened glass substrate in a rotating and inclined manner by using a sprayer so that the surface of the primary roughened glass substrate and the side walls of the longitudinal pits are dispersed with drop-shaped roughening solution, and the roughening solution dispersed on the side walls of the longitudinal pits can transversely corrode the primary roughened glass substrate to obtain a secondary roughened glass substrate with longitudinal and transverse pits; after the impact-resistant paint is uniformly sprayed on the surface of the secondary roughened glass substrate, the impact-resistant paint of the inner layer can inwards penetrate into the longitudinal pits and the transverse pits, so that the contact area between the impact-resistant paint and the secondary roughened glass substrate is effectively improved, after the impact-resistant paint is subjected to ultraviolet curing and thermosetting, the integral shearing resistance of the coating can be effectively improved by the coating in the longitudinal pits, the integral pulling resistance of the coating can be effectively improved by the coating in the transverse pits, the coating and the secondary roughened glass substrate can be tightly connected together, the bonding force of the coating to the secondary roughened glass substrate is effectively improved, and the phenomena of bubbling, warping, deformation and falling are not easy to occur.
3. According to the invention, the glass substrate is subjected to ultrasonic cleaning by adopting a 5wt% ethanol solution at 55 ℃, and then is subjected to alternate cleaning with deionized water and absolute ethyl alcohol for multiple times, so that dirt such as grease, dust and the like on the surface of the glass substrate can be effectively removed, the roughening effect of the roughening solution on the surface of the glass substrate can be improved, and the actual contact area of the impact-resistant coating and the glass substrate can be increased.
4. In the process of curing the impact-resistant coating, the glass is firstly put into a baking oven with the temperature of 75-85 ℃ and is prebaked for 5-10 minutes, so that the solvent on the surface of the coating can be volatilized, and a large number of air holes caused by too fast volatilization of the solvent in the later curing process can be effectively avoided; through Ultraviolet (UV) curing, double bonds in silicone rubber (vinyl silicone resin) monomer molecules can be opened, and linear elastic high polymer materials with low crosslinking degree are polymerized among the molecules; and then the condensed type silicon resin is cured and condensed into a spatial network structure with a highly cross-linked and branched molecular structure through heat curing at 165-195 ℃, so that the impact resistance of the glass is improved.
5. After the anti-impact coating is thermally cured, the anti-impact glass with the coating is sequentially cooled at 95-105 ℃, 55-65 ℃ and normal temperature environment, so that the internal stress of the coating and the residual gaseous solvent in the coating can be gradually released, the film forming effect of the coating can be improved, and the phenomena of warping, deformation, cracking and the like of the coating caused by sudden temperature drop after the coating is cured are prevented.
6. The adhesion promoter added in the invention can improve the adhesive force between the coating and the glass substrate and plays a role of a bridge between the glass substrate and the coating. In the molecular structure of the adhesion promoter, one end is a-Si-O-R group, and when meeting with trace water molecules in the air, the adhesion promoter is hydrolyzed to generate a-Si-OH group which can be subjected to condensation reaction with-OH hydroxyl on the surface of glass to form a firm-Si-O-Si chemical bond (covalent bond). The other end of the molecular structure of the adhesion promoter is-NH (amino), -SH (mercapto) or-OO-C (CH) 3 )＝CH 2 (allyl). One end is-NH (amino group), -SH (sulfhydryl group) which can be condensed with-OH hydroxyl group in the coating organic silicon resin to form firm chemical bond (covalent bond); -OO-C (C)H 3 )＝CH 2 The (allyl) groups are capable of undergoing UV polymerization with the double bonds of the silicone rubber in the silicone resin. Ensures that the coating does not fall off due to thermal expansion and cold contraction and is resistant to boiling, and improves the bonding strength of the coating and the glass substrate.
7. The organic silicon resin molecules adopted by the invention do not contain groups capable of yellowing, so that the risk of yellowing of the coating is avoided; the coating can obviously improve the shock resistance of the glass by more than 90 percent, the hardness is more than 2H, the production yield is ensured, and the cost is reduced; the coating also has other characteristics of organic silicon, such as high and low temperature resistance (-55-250 ℃), weather resistance, water resistance and the like.
Drawings
FIG. 1 is a structural diagram of T-type, D-type, M-type and Q-type silicone resins in the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A preparation method of impact-resistant glass based on chemical pretreatment comprises the following steps:
s1, dissolving 25 parts by weight of T-shaped methyl silicone resin into 30 parts by weight of ethyl acetate, and magnetically stirring for 1 hour until the T-shaped methyl silicone resin is completely dissolved in the ethyl acetate; then adding 5 parts of methyl vinyl silicone resin, 4 parts of aminopropyl triethoxysilane (KH-550), 0.5 part of polyether modified organic silicon and another 30 parts of ethyl acetate in sequence, and magnetically stirring for 2 hours; after stirring, adding 1 part of 1-hydroxy-cyclohexyl-phenyl ketone and 1 part of dibutyltin dilaurate, and magnetically stirring for 0.5 hour to obtain an impact-resistant coating;
s2, placing the glass substrate in an ultrasonic cleaner, ultrasonically shaking for 15min in a 5wt% ethanol solution at 55 ℃, then flushing with clear water until no foam is generated, then alternately cleaning for three times with deionized water and absolute ethyl alcohol, and finally drying with nitrogen; taking out the dried glass substrate, and spraying sulfuric acid and hydrofluoric acid by a sprayer according to the weight ratio of 1: 3, vertically spraying the roughening solution prepared according to the proportion on the surface of the glass substrate until the surface of the glass substrate is uniformly dispersed with the drop-shaped roughening solution, placing the glass substrate in an environment at 45 ℃ for standing treatment for 1.5 hours, and washing and airing to obtain a primary roughened glass substrate with longitudinal pits;
s3, taking out the primary coarsened glass substrate, and spraying sulfuric acid and hydrofluoric acid by a sprayer according to the weight ratio of 1: 3, spraying the roughening solution prepared according to the proportion on the surface of the primary roughened glass substrate in a rotating and inclined manner until the surface of the primary roughened glass substrate and the side walls of the longitudinal pits are scattered with water drop-shaped roughening solution, placing the primary roughened glass substrate scattered with the roughening solution in an environment at 45 ℃ for standing treatment for 1.5 hours, and washing and airing to obtain a secondary roughened glass substrate with longitudinal pits and transverse pits;
s4, taking out the secondary roughened glass substrate, and uniformly spraying the impact-resistant coating prepared in the step S1 on the surface of the secondary roughened glass substrate by using an automatic air spray gun, wherein the thickness of the coating is 11 microns;
s5, placing the glass sprayed with the impact-resistant coating in the step S4 into an oven at 80 ℃, and pre-baking for 8 minutes to volatilize the solvent on the surface of the coating; putting the pre-baked glass into an Ultraviolet (UV) furnace for curing, wherein the UV energy is controlled at 600mJ/cm 2 (ii) a Then putting the glass subjected to ultraviolet curing into an oven at 180 ℃ and curing for 40 minutes; and (2) putting the glass solidified at the temperature of 180 ℃ into an environment at the temperature of 100 ℃, cooling for 25 minutes, putting the glass into an environment at the temperature of 60 ℃, cooling for 20 minutes, finally taking out the glass, naturally cooling to room temperature, and testing the impact resistance of the impact-resistant glass with the coating and the hardness, the adhesiveness, the scrub resistance and the yellowing condition of the coating, wherein the test results are shown in table 1.
Example 2
A preparation method of impact-resistant glass based on chemical pretreatment comprises the following steps:
s1, dissolving 30 parts by weight of T-phenyl silicone resin in 30 parts by weight of ethyl acetate, and magnetically stirring for 1 hour until the T-phenyl silicone resin is completely dissolved in the ethyl acetate; sequentially adding 2 parts of methyl phenyl vinyl silicone resin, 5 parts of gamma-mercaptopropyl trimethoxy silane (KH-590), 1 part of polyester modified organic silicon and the other 30 parts of ethyl acetate, and magnetically stirring for 2 hours; after stirring, adding 0.5 part of 2-hydroxy-2-methyl-1-phenyl-1-acetone and 0.5 part of ethyl orthosilicate, and magnetically stirring for 0.5 hour to obtain an impact-resistant coating;
s2, placing the glass substrate in an ultrasonic cleaner, ultrasonically shaking for 15min in a 5wt% ethanol solution at 55 ℃, then flushing with clear water until no foam is generated, then alternately cleaning for three times with deionized water and absolute ethyl alcohol, and finally drying with nitrogen; taking out the dried glass substrate, and spraying sulfuric acid and hydrofluoric acid by a sprayer according to the weight ratio of 1: 3, vertically spraying the roughening solution prepared according to the proportion on the surface of the glass substrate until the surface of the glass substrate is uniformly dispersed with the drop-shaped roughening solution, placing the glass substrate in an environment at 45 ℃ for standing treatment for 1.5 hours, and washing and airing to obtain a primary roughened glass substrate with longitudinal pits;
s3, taking out the primary coarsened glass substrate, and spraying sulfuric acid and hydrofluoric acid by a sprayer according to the weight ratio of 1: 3, spraying the roughening solution prepared according to the proportion on the surface of the primary roughened glass substrate in a rotating and inclined manner until the surface of the primary roughened glass substrate and the side walls of the longitudinal pits are scattered with water drop-shaped roughening solution, placing the primary roughened glass substrate scattered with the roughening solution in an environment at 45 ℃ for standing treatment for 1.5 hours, and washing and airing to obtain a secondary roughened glass substrate with longitudinal pits and transverse pits;
s4, taking out the secondary roughened glass substrate, and uniformly spraying the impact-resistant coating prepared in the step S1 on the surface of the secondary roughened glass substrate by using an automatic air spray gun, wherein the thickness of the coating is 8 microns;
s5, placing the glass sprayed with the impact-resistant coating in the step S4 into an oven at 80 ℃, and pre-baking for 8 minutes to volatilize the solvent on the surface of the coating; putting the pre-baked glass into an Ultraviolet (UV) furnace for curing, wherein the UV energy is controlled at 500mJ/cm 2 (ii) a Then putting the glass subjected to ultraviolet curing into an oven at 180 ℃ and curing for 40 minutes; putting the glass solidified at 180 ℃ into a ring at 100 DEG CAnd cooling for 25 minutes, putting the glass into an environment at 60 ℃, cooling for 20 minutes, taking out the glass, naturally cooling to room temperature, and testing the impact resistance of the impact-resistant glass with the coating, the hardness, the adhesiveness, the scrub resistance and the yellowing of the coating, wherein the test results are shown in table 1.
Example 3
A preparation method of impact-resistant glass based on chemical pretreatment comprises the following steps:
s1, dissolving 28 parts by weight of T-shaped methyl silicone resin in 30 parts by weight of ethyl acetate, and magnetically stirring for 1 hour until the T-shaped methyl silicone resin is completely dissolved in the ethyl acetate; then adding 3 parts of methyl trifluoro propyl vinyl fluorosilicone resin, 1 part of gamma-mercaptopropyltriethoxysilane (KH-580), 0.1 part of polyether modified organic silicon and the other 30 parts of ethyl acetate in sequence, and magnetically stirring for 2 hours; after stirring, 1.5 parts of 1-hydroxy-cyclohexyl-phenyl ketone and 1.5 parts of dibutyltin dilaurate are added, and magnetic stirring is carried out for 0.5 hour to obtain an impact-resistant coating;
s2, placing the glass substrate in an ultrasonic cleaner, ultrasonically shaking for 15min in a 5wt% ethanol solution at 55 ℃, then flushing with clear water until no foam is generated, then alternately cleaning for three times with deionized water and absolute ethyl alcohol, and finally drying with nitrogen; taking out the dried glass substrate, and spraying sulfuric acid and hydrofluoric acid by a sprayer according to the weight ratio of 1: 3, vertically spraying the roughening solution prepared according to the proportion on the surface of the glass substrate until the surface of the glass substrate is uniformly dispersed with the drop-shaped roughening solution, placing the glass substrate in an environment at 45 ℃ for standing treatment for 1.5 hours, and washing and airing to obtain a primary roughened glass substrate with longitudinal pits;
s3, taking out the primary coarsened glass substrate, and spraying sulfuric acid and hydrofluoric acid by a sprayer according to the weight ratio of 1: 3, spraying the roughening solution prepared according to the proportion on the surface of the primary roughened glass substrate in a rotating and inclined manner until the surface of the primary roughened glass substrate and the side walls of the longitudinal pits are scattered with water drop-shaped roughening solution, placing the primary roughened glass substrate scattered with the roughening solution in an environment at 45 ℃ for standing treatment for 1.5 hours, and washing and airing to obtain a secondary roughened glass substrate with longitudinal pits and transverse pits;
s4, taking out the secondary roughened glass substrate, and uniformly spraying the impact-resistant coating prepared in the step S1 on the surface of the secondary roughened glass substrate by using an automatic air spray gun, wherein the thickness of the coating is 8 microns;
s5, placing the glass sprayed with the impact-resistant coating in the step S4 into an oven at 80 ℃, and pre-baking for 8 minutes to volatilize the solvent on the surface of the coating; putting the pre-baked glass into an Ultraviolet (UV) furnace for curing, wherein the UV energy is controlled to be 550mJ/cm 2 (ii) a Then placing the glass subjected to ultraviolet curing into an oven at 180 ℃ for curing for 40 minutes; and (2) putting the glass solidified at the temperature of 180 ℃ into an environment at the temperature of 100 ℃, cooling for 25 minutes, putting the glass into an environment at the temperature of 60 ℃, cooling for 20 minutes, finally taking out the glass, naturally cooling to room temperature, and testing the impact resistance of the impact-resistant glass with the coating and the hardness, the adhesiveness, the scrub resistance and the yellowing condition of the coating, wherein the test results are shown in table 1.
Example 4
A preparation method of impact-resistant glass based on chemical pretreatment comprises the following steps:
s1, dissolving 20 parts by weight of T-shaped methyl silicone resin into 30 parts by weight of ethyl acetate, and magnetically stirring for 1 hour until the T-shaped methyl silicone resin is completely dissolved in the ethyl acetate; then adding 9 parts of methyl vinyl silicone resin, 3 parts of gamma- (methacryloyloxy) -propyl trimethoxy silane (KH-570), 0.7 part of polydimethylsiloxane and the other 30 parts of ethyl acetate in sequence, and magnetically stirring for 2 hours; after stirring, adding 2.5 parts of 1-hydroxy-cyclohexyl-phenyl ketone and 2.5 parts of dibutyltin dilaurate, and magnetically stirring for 0.5 hour to obtain an impact-resistant coating;
s2, placing the glass substrate in an ultrasonic cleaner, ultrasonically shaking for 15min in a 5wt% ethanol solution at 55 ℃, then flushing with clear water until no foam is generated, then alternately cleaning for three times with deionized water and absolute ethyl alcohol, and finally drying with nitrogen; taking out the dried glass substrate, and spraying sulfuric acid and hydrofluoric acid by a sprayer according to the weight ratio of 1: 3, vertically spraying the roughening solution prepared according to the proportion on the surface of the glass substrate until the surface of the glass substrate is uniformly dispersed with the drop-shaped roughening solution, standing the glass substrate in an environment at 45 ℃ for 1.5 hours, and washing and airing to obtain a primary roughened glass substrate with longitudinal pits;
s3, taking out the primary coarsened glass substrate, and spraying sulfuric acid and hydrofluoric acid by a sprayer according to the proportion of 1: 3, spraying the roughening solution prepared according to the proportion on the surface of the primary roughened glass substrate in a rotating and inclined manner until the surface of the primary roughened glass substrate and the side walls of the longitudinal pits are scattered with water drop-shaped roughening solution, placing the primary roughened glass substrate scattered with the roughening solution in an environment at 45 ℃ for standing treatment for 1.5 hours, and washing and airing to obtain a secondary roughened glass substrate with longitudinal pits and transverse pits;
s4, taking out the secondary roughened glass substrate, and uniformly spraying the impact-resistant coating prepared in the step S1 on the surface of the secondary roughened glass substrate by using an automatic air spray gun, wherein the thickness of the coating is 11 microns;
s5, placing the glass sprayed with the anti-impact paint in the step S4 into an oven at 80 ℃, and pre-baking for 8 minutes to volatilize the solvent on the surface of the coating; putting the pre-baked glass into an Ultraviolet (UV) furnace for curing, wherein the UV energy is controlled to be 700mJ/cm 2 (ii) a Then putting the glass subjected to ultraviolet curing into an oven at 180 ℃ and curing for 40 minutes; and (2) putting the glass solidified at the temperature of 180 ℃ into an environment at the temperature of 100 ℃, cooling for 25 minutes, putting the glass into an environment at the temperature of 60 ℃, cooling for 20 minutes, finally taking out the glass, naturally cooling to room temperature, and testing the impact resistance of the impact-resistant glass with the coating and the hardness, the adhesiveness, the scrub resistance and the yellowing condition of the coating, wherein the test results are shown in table 1.
Comparative examples
A preparation method of impact-resistant glass based on chemical pretreatment comprises the following steps:
s1, sequentially taking 10 parts of D-type methyl phenyl organic silicon resin, 15 parts of organic silicon modified acrylate, 15 parts of tetra-functional polyurethane acrylate and 2 parts of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH-560), and magnetically stirring for 2 hours. After the stirring, 2 parts of 1-hydroxy-cyclohexyl-phenyl-methanone was added and stirred magnetically for 0.5 hour.
S2, spraying the impact resistant paint obtained in S1 on the surface of the prepared glass substrate by an automatic air spray gun, and controlling the film thickness of the paint to be 12 microns.
S3, placing the glass sprayed with the impact-resistant paint in the step S2 into a baking oven at 60 ℃, and pre-baking for 8 minutes to volatilize the solvent on the surface of the coating; putting the pre-baked glass into an Ultraviolet (UV) furnace for curing, wherein the UV energy is controlled at 1100mJ/cm 2 (ii) a And then placing the glass subjected to ultraviolet curing into an oven at 100 ℃, curing for 40 minutes, naturally cooling to room temperature, and testing the impact resistance of the impact-resistant glass with the coating and the hardness, adhesion, scrub resistance and yellowing conditions of the coating, wherein the test results are shown in table 1.
TABLE 1 test results of coated impact resistant glasses and coatings made in examples 1-4 and comparative examples
As can be seen from the test results in table 1 and fig. 1, the impact-resistant glass coating prepared in the comparative example has a small improvement range on the impact resistance of glass, has a low surface hardness, is easily scratched, has poor adhesion and scrub resistance, and is easily yellowed. The impact-resistant glass coating prepared in the embodiments 1 to 4 has a large improvement range of the impact resistance of glass, the impact resistance improvement rate is over 90 percent, the surface hardness of the coating is high, the hardness is over 3H, the coating is scratch-resistant and scratch-resistant, the yield of the process of manufacturing the impact-resistant glass coating is ensured, the adhesiveness and the washing and brushing resistance are good, the coating is not easy to fall off, and the coating is not easy to yellow.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (7)
1. A preparation method of impact-resistant glass based on chemical pretreatment is characterized by comprising the following steps:
s1, dissolving 20-30 parts by weight of condensed type silicone resin into 28-32 parts by weight of solvent, and magnetically stirring for 0.5-1.5 hours until the condensed type silicone resin is completely dissolved in the solvent; then sequentially adding 2-10 parts of vinyl silicone resin, 1-5 parts of adhesion promoter, 0.1-1 part of flatting agent and 28-32 parts of solvent, and magnetically stirring for 1.5-2.5 hours; after stirring, adding 1-5 parts of curing agent, and magnetically stirring for 0.2-0.8 hour to obtain the impact-resistant coating;
the condensed type silicon resin is one or a mixture of more than two of T-type methyl silicon resin, D-type methyl silicon resin, T-type phenyl silicon resin, D-type phenyl silicon resin and D-type methyl phenyl silicon resin;
the curing agent comprises a light curing agent and a heat curing agent; the light curing agent is one or a mixture of more than two of benzophenone, 1-hydroxy-cyclohexyl-phenyl ketone and 2-hydroxy-2-methyl-1-phenyl-1-acetone; the thermal curing agent is one or a mixture of more than two of ethyl orthosilicate, dibutyltin dilaurate and n-butyl borate;
the adhesion promoter is one or the mixture of more than two of gamma-aminopropyl triethoxysilane, gamma- (methacryloyloxy) -propyl trimethoxysilane, gamma-mercaptopropyl triethoxysilane and gamma-mercaptopropyl trimethoxysilane;
s2, sequentially cleaning and drying the surface of the glass substrate; taking out the dried glass substrate, vertically spraying the roughening solution on the surface of the glass substrate by using a sprayer until the surface of the glass substrate is uniformly dispersed with the water-drop roughening solution, standing the glass substrate in an environment of 35-55 ℃ for 0.5-2.5 hours, and washing and airing to obtain a primary roughened glass substrate with longitudinal pits;
s3, taking out the primarily roughened glass substrate, spraying the roughening solution on the primarily roughened glass substrate in a rotary inclined manner by a sprayer until the surface of the primarily roughened glass substrate and the side walls of the longitudinal pits are scattered with water drop-shaped roughening solution, placing the primarily roughened glass substrate with the roughening solution scattered in the primarily roughened glass substrate in an environment with the temperature of 35-55 ℃ for standing treatment for 0.5-2.5 hours, and washing and airing to obtain a secondary roughened glass substrate with longitudinal pits and transverse pits;
s4, taking out the secondary roughened glass substrate, and uniformly spraying the impact-resistant coating prepared in the step S1 on the surface of the secondary roughened glass substrate by using an automatic air spray gun, wherein the thickness of the coating is 8-12 microns;
s5, placing the glass sprayed with the anti-impact paint in the step S4 into a baking oven with the temperature of 75-85 ℃ for pre-baking for 5-10 minutes; placing the pre-baked glass into an ultraviolet UV furnace for curing, wherein the ultraviolet energy is controlled at 500-700mJ/cm 2 (ii) a And then placing the glass into an oven with the temperature of 165-195 ℃, curing for 30-50 minutes, and cooling to room temperature step by step to obtain the impact-resistant glass.
2. A process for the preparation of impact-resistant glass based on chemical pretreatment according to claim 1, characterized in that: the roughening solution in steps S2 and S3 is prepared from sulfuric acid and hydrofluoric acid in a ratio of 1: 2-5.
3. The method for preparing impact-resistant glass based on chemical pretreatment according to claim 1, wherein the specific method for sequentially cleaning and drying the surface of the glass substrate in the step S2 comprises the following steps: the glass substrate is placed in an ultrasonic cleaner, ultrasonically vibrated for 15min in 5wt% ethanol solution at 55 ℃, washed by clean water until no foam is generated, then alternately washed three times by deionized water and absolute ethyl alcohol, and finally dried by nitrogen.
4. The method for preparing impact-resistant glass based on chemical pretreatment according to claim 1, wherein the step of cooling to room temperature in step S5 comprises the following steps: putting the glass solidified at the temperature of 165-195 ℃ into the environment of 95-105 ℃, cooling for 10-35 minutes, putting the glass into the environment of 55-65 ℃, cooling for 8-32 minutes, and finally taking out the glass and naturally cooling to the room temperature.
5. A method for preparing impact-resistant glass based on chemical pretreatment according to claim 1, characterized in that: the vinyl silicone resin is one or a mixture of more than two of methyl vinyl silicone resin, methyl phenyl vinyl silicone resin and methyl trifluoro propyl vinyl fluorosilicone resin.
6. A method for preparing impact-resistant glass based on chemical pretreatment according to claim 1, characterized in that: the leveling agent is one or a mixture of more than two of polyether modified organic silicon, polyester modified organic silicon, polydimethylsiloxane, fluorine modified acrylate and acrylate copolymer.
7. A process for the preparation of impact-resistant glass based on chemical pretreatment according to claim 1, characterized in that: the solvent is one or a mixture of more than two of ethyl acetate, butyl acetate, isopropanol, n-butanol, ethanol, ethylene glycol monobutyl ether and propylene glycol methyl ether.
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