CN107033650B - A kind of preparation method of antifouling antibacterial composite coating - Google Patents

A kind of preparation method of antifouling antibacterial composite coating Download PDF

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CN107033650B
CN107033650B CN201710315980.8A CN201710315980A CN107033650B CN 107033650 B CN107033650 B CN 107033650B CN 201710315980 A CN201710315980 A CN 201710315980A CN 107033650 B CN107033650 B CN 107033650B
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alcohol
microballoon
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sio
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CN107033650A (en
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陈大华
秦玉林
唐少俊
潘立升
洪丽
熊建民
茆俊峰
熊辉
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Chery Automobile Co Ltd
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SAIC Chery Automobile Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16Antifouling paints; Underwater paints
    • C09D5/1606Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612Non-macromolecular compounds
    • C09D5/1618Non-macromolecular compounds inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances

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  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

The present invention relates to a kind of preparation methods of antifouling antibacterial composite coating, comprising the following steps: (1) disperses formation solution (A) in alcohol/aqueous solution for ethyl orthosilicate;Ammonium hydroxide is added in alcohol, is formed alcohol ammonia solution (B);Alcohol ammonia solution (B) is added in solution (A) and is stirred;It is then allowed to stand to obtain the nanometer spherical SiO in solution (C) and solution (C)2Particle;(2) by Nano-meter SiO_2 obtained above2Microballoon is scattered in containing SnCl2·2H2Sensitized treatment is carried out in the acidic aqueous solution of O, obtains being adsorbed with Sn2+SiO2Microballoon (D), will be adsorbed with Sn2+SiO2Microballoon (D) is dispersed in water and AgNO is added3Solution and reducing agent obtain carrying Ag Nano-meter SiO_22Microballoon;(3) by load Ag Nano-meter SiO_2 obtained above2Microballoon is scattered in alcohol solution, and the hydrolyzed silane solution containing perfluoroalkyl is then added into the solution, obtains antifouling antibacterial composite coating.

Description

A kind of preparation method of antifouling antibacterial composite coating
Technical field
The invention belongs to antifouling antibacterial technical field of paint preparation, more particularly to a kind of Car-use Fabric surface that is used for prevent The coating of dirty antibacterial processing.
Background technique
Automotive interior is the environment relatively sealed, it is easy to breed a large amount of bacterium, especially trickle down in vehicle The sweat stain etc. that interior fruit juice, swill and hand contact site leaves creates condition for the breeding of bacterium.Hand frequently contacts Position and air-conditioner air outlet germ contamination are the most serious, such as steering wheel, shift handle, seat, handle, air outlet, and vehicle age Longer, interior body surface total plate count is higher.It shows according to investigations, the private car in 1 year and 3 years vehicle ages, steering wheel, shift hand Total number of bacteria at handle and air-conditioner air outlet three is respectively 95000 cfu/cm2、210900 cfu/cm2、83000 cfu/cm2With 122000 cfu/cm2、237000 cfu/cm2、90100 cfu/cm2, much higher than common objects surface colony sum reference value (< 500 cfu/cm2), it is occupant's health care belt to endanger.
Currently, solved to solve the problems, such as that interior total number of bacteria is severely exceeded frequently with the method for medicinal alcohol wiping, but It is, although total plate count meeting rapid drawdown after being wiped using medicinal alcohol, for its inside gadget surface colony of the car compared with long vehicle age Sum still exceeds standard reference value.In addition, having the hydrophobic product for Car-use Fabric on the market, after such product The processing easy to clean such as the fruit juice on its surface is trickled down, but still cannot fundamentally solve the problems, such as bacterial reproduction;A kind of commercially available light Catalysis automatically cleaning product can play the role of sterilization and decomposing organic matter after automobile interior decoration coating, but such product needs purple Outer light irradiation excitation, effect are limited.In view of the deficiencies of the prior art, propose that a kind of antifouling antibacterial composite coating is used to control automobile The solution of inside gadget surface colony sum.
Summary of the invention
In order to solve above-mentioned technical problem, the present invention devises a kind of preparation side of antifouling antibacterial composite coating Method can form sterilization nonpolluting coating on automotive upholstery surface.
In order to solve above-mentioned technical problem, present invention employs following scheme:
A kind of preparation method of antifouling antibacterial composite coating, which comprises the following steps:
(1) Nano-meter SiO_2 is prepared2Microballoon: it disperses ethyl orthosilicate in alcohol/aqueous solution and forms solution A;Ammonium hydroxide is added In alcohol, alcohol ammonia solution B is formed;Alcohol ammonia solution B is added in solution A and is stirred;It is then allowed to stand, obtains being dispersed with nanometer spherical The solution (C) of SiO2 particle separates the solution (C) for being dispersed with nanometer spherical SiO2 particle, obtains nanometer spherical SiO2 Particle;
(2) preparation carries Ag Nano-meter SiO_22Microballoon: by Nano-meter SiO_2 obtained above2Microballoon is scattered in containing SnCl2·2H2O's Sensitized treatment is carried out in acidic aqueous solution, is stood, and separation obtains being adsorbed with Sn2+SiO2Microballoon D will be adsorbed with Sn2+SiO2 Microballoon D is dispersed in water and AgNO is added3Solution and reducing agent are stood, separation, obtain carrying Ag Nano-meter SiO_22Microballoon;
(3) by load Ag Nano-meter SiO_2 obtained above2Microballoon is scattered in alcohol solution, is then added and is contained into the solution There is a hydrolyzed silane solution of perfluoroalkyl, realizes perfluoroalkyl silanes to being loaded with Ag nano particles SiO2The surface modification of microballoon, obtains To antifouling antibacterial composite coating.
Further, the solution A in step (1), mass ratio shared by water are 0.4%~2.6%, mass ratio shared by ethyl orthosilicate It is 1.8%~2.0%, surplus is alcohol.
Further, in step (1), NH in alcohol ammonia solution B3Mass percentage is 3.1%~7.2%, and surplus is alcohol.
Further, in step (1), at room temperature, alcohol ammonia solution B is added in solution A and is given simultaneously and is stirred, stirring speed Degree is 500~1000 turns/min;Alcohol ammonia solution B is added completely into after solution A persistently stirs 30~120min again.
Further, alcohol ammonia solution B is added dropwise in addition solution A in step (1) with the speed of 20~45 μ l/min.
Further, in step (1), alcohol ammonia solution B is added in solution A after persistently stirring, opening stands 24~72h and obtains Solution C is centrifugated and 1~3 hour dry at 100~180 DEG C to obtained solid product by solution C, and obtaining partial size is 10 The Nano-meter SiO_2 of~75nm2Microballoon.
Further, in step (2), by SnCl2·2H2O is added in acidic aqueous solution and forms SnCl2Mass percentage is 0.08%~0.12% solution, with 800~1200 revs/min of revolving speed, after 15~30 minutes solution of magnetic agitation thereto Nano-meter SiO_2 is added2Microballoon, then magnetic agitation disperse 30~60 minutes formation mixed solutions, SiO in mixed solution2Microspheres quality hundred Dividing content is 0.15%~0.25%;Gained mixed solution is stood, is then centrifuged for isolated being adsorbed with Sn2+SiO2Microballoon D.
Further, in step (2), the acidic aqueous solution is hydrochloric acid deionized water solution, pH value 2.5.
Further, in step (2), Sn will be adsorbed with2+SiO2Microballoon D is scattered in deionized water or distilled water, absorption There is Sn2+SiO2The additional amount and deionized water of microballoon D or the mass ratio of distilled water are 1:5, and AgNO3 solution is then added, The mass ratio of AgNO3 and the aqueous solution for the SiO2 microballoon D for being adsorbed with Sn2+ in middle AgNO3 solution are 0.005:1~0.032: After 1, stirring 30~90 minutes, reducing agent is added, is stirred for 1~3 hour after adding reducing agent, then, is centrifugally separating to obtain Load has the Nano-meter SiO_2 of Ag particle2Microballoon, wherein the mass percentage of silver carrying amount is 5%~8%.
Further, in step (2), AgNO3 solution and reducing agent are added in a manner of dropwise addition.
Further, the reducing agent is hydrazine or formaldehyde, the additional amount and AgNO of reducing agent3Molar ratio be 1:1.4~ 1:2.0.
Further, in step (3), above-mentioned load Ag there is into nanoparticle SiO2Microballoon, which is scattered in alcohol solution, forms solid content 10%~20% solution I;Perfluoroalkyl silanes are added in alcohol solution, and appropriate acid-catalyzed hydrolysis is added, obtain solution II; Solution I is mixed according to a certain percentage with solution II, obtains antifouling antibacterial composite coating;In this step, alcohol in alcohol solution It is 8:1~14:1 with water mixed volume ratio.
Further, in step (3), perfluoroalkyl silanes and alcohol/aqueous solution are mixed, wherein matter shared by perfluoroalkyl silanes For amount than being 1.5%~3%, it is 4.5~6 that acid, which is then added, and adjusts the solution ph, small with 200~500 revs/min of stirrings 4~24 When obtain solution II;The perfluoroalkyl silanes structural formula are as follows:
It is 1~3, a is 0~2 that wherein m, which is 2~30, n,;For perfluor carbochain or perfluoroether chain,For hydrolyzable groups halogen Dai Ji or alkoxy;ForOr alkoxy;The acid is the mixture of one of acetic acid, citric acid or both.
Further, in step (3), the perfluoroalkyl silanes structural formula are as follows:
Wherein the value range of m is 2~30, preferably n=1, preferably a=0 or 1, most preferably a=0;For perfluor carbochain or entirely Fluorinated ether chain, such asOrOrFor can water Group halo or alkoxy are solved,ForOr alkoxy, under acid catalysis,In halogeno-groupAnd alcoxyl BaseIt hydrolyzes, forms the silanol with the Long carbon chain containing F
Further, solution I is mixed with solution II according to mass ratio 1:1~1:2, with 200~500 revs/min stirring 0.5~ 4 hours.
Further, the water is deionized water or distilled water;The alcohol is ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol One of or wherein several mixtures.
The preparation method of the antifouling antibacterial composite coating has the advantages that
(1) present invention uses Nano-meter SiO_22Microballoon is carrier, deposits nano-Ag particles on its surface, and with perfluoroalkyl silicon Alkane hydrolysate perfluoroalkyl modifies its surface, obtains having hydrophobic and fungistatic effect nanocomposite.Using Alcohol/aqueous solution containing the nanocomposite often touches position to automotive upholstery and carries out plated film, and average water contact can be obtained Angle is remarkably improved automotive upholstery not less than 110 °, the film layer of staphylococcus aureus and 95% or more Escherichia coli bacteriostasis rate Property easy to clean and reduce inside gadget surface total plate count.
(2) SiO of the present invention2It is microsphere supported while being loaded with hydrophobic grouping and nanometer Ag, in the form of a paint using assigning simultaneously Give that automobile interior decoration is antifouling and bacteriostasis, the technology raw material sources extensively, using simple, significant effect.
Detailed description of the invention
Fig. 1: the antifouling antibacterial composite coating preparation process flow of the present invention.
Specific embodiment
With reference to the accompanying drawing and embodiment, the present invention will be further described:
Embodiment one: the present embodiment provides a kind of preparation methods of antifouling antibacterial composite coating, comprising the following steps:
(1) it disperses ethyl orthosilicate in ethanol distillation water mixed liquid and obtains solution A, wherein ethyl orthosilicate quality hundred Dividing content is 1.88%, and distilled water mass percentage is 2.53%, and surplus is ethyl alcohol;By concentrated ammonia liquor (concentration 28%-30%, with It similarly hereinafter) is added in ethyl alcohol, obtains NH3The alcohol ammonia solution B that mass percentage is 6.60%;By alcohol ammonia solution B with 20 μ l/min's Speed is added in solution A, while being stirred with 1000 revs/min, persistently stirs 30 after alcohol ammonia solution B is all added in solution A Minute, then open standing obtains solution C in 24 hours, solution C is centrifugated, then by obtained solid product at 100 DEG C It is 3 hours dry, obtain the SiO that partial size is about 75nm2Microballoon.
(2) by SnCl2·2H2O is added in aqueous hydrochloric acid solution, forms SnCl2The solution that mass percentage is 0.08%, it is molten Liquid pH value was 2.5, with mixing speed magnetic agitation 15 minutes of 800 revs/min;Then Nano-meter SiO_2 is added2Microballoon, SiO2Microballoon Additional amount accounts for the 0.15% of solution gross mass, is persistently dispersed with stirring 30~60 minutes, stands 30 minutes after stirring, centrifugation point From obtaining being adsorbed with Sn2+SiO2Microballoon D.
(3) it disperses product D in deionized water, the additional amount of product D and the mass ratio of deionized water are 1:5, then The AgNO of 6mmol/L is added dropwise3Solution, wherein AgNO3AgNO in solution3Be adsorbed with Sn2+SiO2Microballoon D's is water-soluble The mass ratio of liquid is 0.01:1, after stirring 30~90 minutes, then formaldehyde is added dropwise into solution, formaldehyde additional amount and AgNO3 Molar ratio be 1:2.0, be stirred for 1~3 hour after adding reducing agent, be then centrifuged, obtain product E, that is, load There is the Nano-meter SiO_2 of Ag particle2Microballoon, carrying Ag amount (mass percentage) is about 5%~8%.
(4) SiO of Ag nano particles will be loaded with2Microballoon E, which is scattered in ethyl alcohol/deionized water solution, to be formed admittedly The solution I of content 10%~20%, wherein alcohol and deionized water mixed volume ratio are 8:1~14:1;By perfluoroalkyl silanesIt is mixed with ethyl alcohol/deionized water solution, wherein perfluoroalkyl silanes institute Account for mass ratio be 1.5%~3%, then be added acetic acid adjust solution ph be 4.5~6, with 200~500 revs/min stirring 4~ Obtain solution II within 24 hours, wherein alcohol and water mixed volume ratio are 8~14:1;Solution I and solution II are mixed according to mass ratio 1:1 It closes, is stirred 0.5 hour with 200 revs/min and obtain antifouling antibacterial composite coating.
Position is often touched to automotive upholstery using the antifouling antibacterial composite coating and carries out plated film, average water contact can be obtained Angle is about the film layer of 111 °, staphylococcus aureus bacteriostasis rate 96%, Escherichia coli bacteriostasis rate 99%, is remarkably improved automobile interior decoration The property easy to clean of part and the total plate count for reducing inside gadget surface.
Embodiment two: the present embodiment provides a kind of preparation methods of antifouling antibacterial composite coating, comprising the following steps:
(1) it disperses ethyl orthosilicate in ethanol distillation water mixed liquid and obtains solution A, wherein ethyl orthosilicate quality hundred Dividing content is 1.90%, and distilled water mass percentage is 1.63%, and surplus is ethyl alcohol;Concentrated ammonia liquor is added in ethyl alcohol, NH is obtained3 The alcohol ammonia solution B that mass percentage is 5.55%;Alcohol ammonia solution B is added in solution A with the speed of 25 μ l/min, while with 800 revs/min of stirrings are persistently stirred 60 minutes after alcohol ammonia solution B is all added in solution A, then open to stand 48 hours Solution C is obtained, solution C is centrifugated, then that obtained solid product is 1.5 hours dry at 120 DEG C, obtaining partial size is about The SiO of 63nm2Microballoon.
(2) by SnCl2·2H2O is added in aqueous hydrochloric acid solution, forms SnCl2The solution that mass percentage is 0.10%, it is molten Liquid pH value was 2.5, with mixing speed magnetic agitation 18 minutes of 900 revs/min;Then system is added obtains Nano-meter SiO_22Microballoon, SiO2Microballoon additional amount accounts for the 0.18% of solution gross mass, is persistently dispersed with stirring 40 minutes, stands 30 minutes after stirring, from The heart is isolated to be adsorbed with Sn2+SiO2Microballoon D.
(3) it disperses product D in deionized water, the additional amount of product D and the mass ratio of deionized water are 1:5, then The AgNO3 solution of 6mmol/L is added dropwise, wherein the water of the AgNO3 in AgNO3 solution and the SiO2 microballoon D for being adsorbed with Sn2+ The mass ratio of solution is 0.013:1, after stirring 50 minutes, then formaldehyde is added dropwise into the solution, formaldehyde additional amount and AgNO3 Molar ratio be 1:1.6, be stirred for 1.5 hours after adding reducing agent, be then centrifuged, obtain product E, i.e., load have The Nano-meter SiO_2 of Ag particle2Microballoon, silver carrying amount (mass percentage) is about 6.2%.
(4) Ag nano particles SiO will be loaded with2Microballoon, which is scattered in ethyl alcohol/deionized water solution, forms the molten of solid content 15% Liquid I, wherein alcohol and water mixed volume ratio are 9:1;By perfluoroalkyl silanes With ethyl alcohol/deionized water solution mixing, wherein mass ratio shared by perfluoroalkyl silanes is 1.8%, and second acid-conditioning solution is then added PH value is 5, is stirred 6 hours with 300 revs/min and obtains solution II, and wherein alcohol and water mixed volume ratio are 9:1;By solution I with it is molten Liquid II is mixed according to mass ratio 1:1.5, is stirred 1 hour with 400 revs/min and is obtained antifouling antibacterial composite coating.
Position is often touched to automotive upholstery using the antifouling antibacterial composite coating and carries out plated film, it is flat that water contact angle can be obtained It is the film layer of 114 °, staphylococcus aureus bacteriostasis rate 96.8%, Escherichia coli bacteriostasis rate 99.5%, is remarkably improved in automobile The property easy to clean of gadget and the total plate count for reducing inside gadget surface.
Embodiment three: the present embodiment provides a kind of antifouling antibacterial composite coating preparation methods, comprising the following steps:
(1) it disperses ethyl orthosilicate in ethanol distillation water mixed liquid and obtains solution A, wherein ethyl orthosilicate quality hundred Dividing content is 1.91%, and distilled water mass percentage is 1.03%, and surplus is ethyl alcohol;Concentrated ammonia liquor is added in ethyl alcohol, NH is obtained3 The alcohol ammonia solution B that mass percentage is 4.39%;Alcohol ammonia solution B is added in solution A with the speed of 30 μ l/min, while with 500 revs/min of stirrings are persistently stirred 90 minutes after alcohol ammonia solution B is all added in solution A, then open to stand 48 hours Solution C is obtained, solution C is centrifugated, then that obtained solid product is 3 hours dry at 100 DEG C, obtaining partial size is about The SiO of 24nm2Microballoon.
(2) by SnCl2·2H2O is added in aqueous hydrochloric acid solution, forms SnCl2The solution that mass percentage is 0.12%, it is molten Liquid pH value was 2.5, with mixing speed magnetic agitation 15 minutes of 1100 revs/min;Then nanometer obtained in step on being added SiO2Microballoon, SiO2Microballoon additional amount accounts for the 0.20% of solution gross mass, is persistently dispersed with stirring 60 minutes, 30 are stood after stirring Minute, it is centrifugally separating to obtain and is adsorbed with Sn2+SiO2Microballoon D.
(3) it disperses product D in deionized water, the additional amount of product D and the mass ratio of deionized water are 1:5, then The AgNO3 solution of 6mmol/L is added dropwise, wherein the water of the AgNO3 in AgNO3 solution and the SiO2 microballoon D for being adsorbed with Sn2+ The mass ratio of solution is 0.014:1, after stirring 70 minutes, then hydrazine is added dropwise into solution, hydrazine additional amount and AgNO3's Molar ratio is to be stirred for 3 hours after 1:1.8 adds reducing agent, is then centrifuged, obtains product E, i.e. load has Ag The Nano-meter SiO_2 of grain2Microballoon, silver carrying amount (mass percentage) is about 7%.
(4) Ag nano particles SiO will be loaded with2Microballoon, which is scattered in isopropanol/distilled water solution, forms the molten of solid content 20% Liquid I, wherein alcohol and water mixed volume ratio are 14:1;By perfluoroalkyl silanes With isopropanol/distilled water solution mixing, wherein mass ratio shared by perfluoroalkyl silanes is 3%, and citric acid regulating solution is then added PH value is 5.5, is stirred 24 hours with 500 revs/min and obtains solution II, and wherein alcohol and water mixed volume ratio are 14:1;By solution I It is mixed with solution II according to mass ratio 1:2, is stirred 4 hours with 500 revs/min and obtain antifouling antibacterial composite coating.
Position is often touched to automotive upholstery using the antifouling antibacterial composite coating and carries out plated film, average water contact can be obtained Angle is about the film layer of 116 °, staphylococcus aureus bacteriostasis rate 98%, Escherichia coli bacteriostasis rate 100%, is remarkably improved in automobile The property easy to clean of gadget and the total plate count for reducing inside gadget surface.
Example IV: the present embodiment provides a kind of antifouling antibacterial composite coating preparation methods, comprising the following steps:
(1) it disperses ethyl orthosilicate in ethanol distillation water mixed liquid and obtains solution A, wherein ethyl orthosilicate quality hundred Dividing content is 1.92%, and distilled water mass percentage is 0.41%, and surplus is ethyl alcohol;Concentrated ammonia liquor is added in ethyl alcohol, NH is obtained3 The alcohol ammonia solution B that mass percentage is 3.09%;Solution B is added in solution A with the speed of 45 μ l/min, while with 600 Turn/min stirring, persistently stir 120min after solution B is all added in solution A, then open stand obtains solution C for 24 hours, will Solution C centrifuge separation, it is then that obtained solid product is 1.5 hours dry at 120 DEG C, obtain the SiO that partial size is about 15nm2It is micro- Ball.
(2) by SnCl2·2H2O is added in aqueous hydrochloric acid solution, forms SnCl2The solution that mass percentage is 0.12%, it is molten Liquid pH value was 2.5, with mixing speed magnetic agitation 20 minutes of 1200 revs/min;Then Nano-meter SiO_2 obtained is walked on being added2 Microballoon, SiO2Microballoon additional amount accounts for the 0.25% of solution gross mass, is persistently dispersed with stirring 60 minutes, and 30 points are stood after stirring Clock is centrifugally separating to obtain and is adsorbed with Sn2+SiO2Microballoon D.
(3) it disperses product D in deionized water, the additional amount of product D and the mass ratio of deionized water are 1:5, then The AgNO3 solution of 6mmol/L is added dropwise, wherein the water of the AgNO3 in AgNO3 solution and the SiO2 microballoon D for being adsorbed with Sn2+ The mass ratio of solution is 0.016:1, after stirring 90 minutes, then hydrazine is added dropwise into solution, hydrazine additional amount and AgNO3's Molar ratio is to be stirred for 3 hours after 1:2.0 adds reducing agent, is then centrifuged, obtains product E, i.e. load has Ag The Nano-meter SiO_2 of grain2Microballoon, silver carrying amount (mass content) is about 8%.
(4) Ag nano particles SiO will be loaded with2Microballoon, which is scattered in isopropanol/distilled water solution, forms the molten of solid content 20% Liquid I, wherein alcohol and water mixed volume ratio are 14:1;By perfluoroalkyl silanes With isopropanol/distilled water solution mixing, wherein mass ratio shared by perfluoroalkyl silanes is 2.8%, and it is molten that citric acid adjusting is then added Liquid pH value is 5.4, is stirred 24 hours with 500 revs/min and obtains solution II, and wherein alcohol and water mixed volume ratio are 14:1;It will be molten Liquid I is mixed with solution II according to mass ratio 1:2, is stirred 4 hours with 500 revs/min and is obtained antifouling antibacterial composite coating.
Position is often touched to automotive upholstery using the antifouling antibacterial composite coating and carries out plated film, average water contact can be obtained Angle is about the film layer of 113 °, staphylococcus aureus bacteriostasis rate 99%, Escherichia coli bacteriostasis rate 100%, is remarkably improved in automobile The property easy to clean of gadget and the total plate count for reducing inside gadget surface.
Embodiment five: the present embodiment provides a kind of antifouling antibacterial composite coating preparation methods, comprising the following steps:
(1) it disperses ethyl orthosilicate in ethanol distillation water mixed liquid and obtains solution A, wherein ethyl orthosilicate quality hundred Dividing content is 1.92%, and distilled water mass percentage is 0.41%, and surplus is ethyl alcohol;Concentrated ammonia liquor is added in ethyl alcohol, NH is obtained3 The alcohol ammonia solution B that mass percentage is 3.09%;Solution B is added in solution A with the speed of 45 μ l/min, while with 600 Turn/min stirring, persistently stir 120min after solution B is all added in solution A, then open stand obtains solution C for 24 hours, will Solution C centrifuge separation, it is then that obtained solid product is 1.5 hours dry at 120 DEG C, obtain the SiO that partial size is about 15nm2It is micro- Ball.
(2) by SnCl2·2H2O is added in aqueous hydrochloric acid solution, forms SnCl2The solution that mass percentage is 0.12%, it is molten Liquid pH value was 2.5, with mixing speed magnetic agitation 20 minutes of 1200 revs/min;Then Nano-meter SiO_2 obtained is walked on being added2 Microballoon, SiO2Microballoon additional amount accounts for the 0.25% of solution gross mass, is persistently dispersed with stirring 60 minutes, and 30 points are stood after stirring Clock is centrifugally separating to obtain and is adsorbed with Sn2+SiO2Microballoon D.
(3) it disperses product D in deionized water, the additional amount of product D and the mass ratio of deionized water are 1:5, then The AgNO of 6mmol/L is added dropwise3Solution, wherein AgNO3AgNO in solution3Be adsorbed with Sn2+SiO2Microballoon D's is water-soluble The mass ratio of liquid is 0.005:1, and stirring after forty minutes, then hydrazine is added dropwise into solution, hydrazine additional amount and AgNO3Rub You are stirred for 3 hours after adding reducing agent, are then centrifuged, obtain product E, is i.e. load has Ag than being 1:1.4 The Nano-meter SiO_2 of grain2Microballoon, silver carrying amount (mass content) is about 5%.
(4) Ag nano particles SiO will be loaded with2Microballoon, which is scattered in isopropanol/distilled water solution, forms the molten of solid content 18% Liquid I, wherein alcohol and water mixed volume ratio are 12:1;By perfluoroalkyl silanes With isopropanol/distilled water solution mixing, wherein mass ratio shared by perfluoroalkyl silanes is 2.0%, and it is molten that citric acid adjusting is then added Liquid pH value is 5.0, is stirred 24 hours with 500 revs/min and obtains solution II, and wherein alcohol and water mixed volume ratio are 14:1;It will be molten Liquid I is mixed with solution II according to mass ratio 1:2, is stirred 4 hours with 500 revs/min and is obtained antifouling antibacterial composite coating.
Position is often touched to automotive upholstery using the antifouling antibacterial composite coating and carries out plated film, water mean exposure can be obtained Angle is about the film layer of 113 °, staphylococcus aureus bacteriostasis rate 95.6%, Escherichia coli bacteriostasis rate 100%, is remarkably improved automobile The property easy to clean of inside gadget and the total plate count for reducing inside gadget surface.
Embodiment six: the present embodiment provides a kind of antifouling antibacterial composite coating preparation methods, comprising the following steps:
(1) it disperses ethyl orthosilicate in ethanol distillation water mixed liquid and obtains solution A, wherein ethyl orthosilicate quality hundred Dividing content is 1.91%, and distilled water mass percentage is 1.03%, and surplus is ethyl alcohol;Concentrated ammonia liquor is added in ethyl alcohol, NH is obtained3 The alcohol ammonia solution B that mass percentage is 4.39%;Alcohol ammonia solution B is added in solution A with the speed of 30 μ l/min, while with 500 revs/min of stirrings are persistently stirred 90 minutes after alcohol ammonia solution B is all added in solution A, then open to stand 48 hours Solution C is obtained, solution C is centrifugated, then that obtained solid product is 3 hours dry at 100 DEG C, obtaining partial size is about The SiO of 24nm2Microballoon.
(2) by SnCl2·2H2O is added in aqueous hydrochloric acid solution, forms SnCl2The solution that mass percentage is 0.12%, it is molten Liquid pH value was 2.5, with mixing speed magnetic agitation 15 minutes of 1100 revs/min;Then nanometer obtained in step on being added SiO2Microballoon, SiO2Microballoon additional amount accounts for the 0.20% of solution gross mass, is persistently dispersed with stirring 30 minutes, 30 are stood after stirring Minute, it is centrifugally separating to obtain and is adsorbed with Sn2+SiO2Microballoon D.
(3) it disperses product D in deionized water, the additional amount of product D and the mass ratio of deionized water are 1:5, then The AgNO of 6mmol/L is added dropwise3Solution, wherein AgNO3AgNO in solution3Be adsorbed with Sn2+SiO2Microballoon D's is water-soluble The mass ratio of liquid is 0.032:1, after stirring 30 minutes, then hydrazine is added dropwise into solution, hydrazine additional amount and AgNO3Rub You are stirred for 3 hours after adding reducing agent, are then centrifuged, obtain product E, is i.e. load has Ag particle than being 1:1.2 Nano-meter SiO_22Microballoon, silver carrying amount (mass percentage) is about 8%.
(4) Ag nano particles SiO will be loaded with2Microballoon, which is scattered in isopropanol/distilled water solution, forms the molten of solid content 10% Liquid I, wherein alcohol and water mixed volume ratio are 10:1;By perfluoroalkyl silanes With isopropanol/distilled water solution mixing, wherein mass ratio shared by perfluoroalkyl silanes is 3%, and citric acid regulating solution is then added PH value is 5.0, is stirred 24 hours with 500 revs/min and obtains solution II, and wherein alcohol and water mixed volume ratio are 12:1;By solution I It is mixed with solution II according to mass ratio 1:2, is stirred 4 hours with 500 revs/min and obtain antifouling antibacterial composite coating.
Position is often touched to automotive upholstery using the antifouling antibacterial composite coating and carries out plated film, water mean exposure can be obtained Angle is about the film layer of 116 °, staphylococcus aureus bacteriostasis rate 98%, Escherichia coli bacteriostasis rate 100%, is remarkably improved in automobile The property easy to clean of gadget and the total plate count for reducing inside gadget surface.
Above in conjunction with attached drawing, an exemplary description of the invention, it is clear that realization of the invention is not by aforesaid way Limitation, as long as use the inventive concept and technical scheme of the present invention carry out various improvement, or it is not improved will be of the invention Conception and technical scheme directly apply to other occasions, be within the scope of the invention.

Claims (10)

1. a kind of preparation method of antifouling antibacterial composite coating, which comprises the following steps:
(1) Nano-meter SiO_2 is prepared2Microballoon: formation solution (A) in alcohol/aqueous solution is dispersed by ethyl orthosilicate;Alcohol is added in ammonium hydroxide In, it is formed alcohol ammonia solution (B);Alcohol ammonia solution (B) is added in solution (A) and is stirred;It is then allowed to stand, obtains being dispersed with nanosphere The solution (C) of shape SiO2 particle separates the solution (C) for being dispersed with nanometer spherical SiO2 particle, obtains nanometer spherical SiO2 particle;
(2) preparation carries Ag Nano-meter SiO_22Microballoon: by Nano-meter SiO_2 obtained above2Microballoon is scattered in containing SnCl2·2H2The acid water of O Sensitized treatment is carried out in solution, is stood, and separation obtains being adsorbed with Sn2+SiO2Microballoon (D), will be adsorbed with Sn2+SiO2Microballoon (D) it is dispersed in water and AgNO is added3Solution and reducing agent are stood, separation, obtain carrying Ag Nano-meter SiO_22Microballoon;
By SnCl2·2H2O is added in acidic aqueous solution and forms SnCl2The solution that mass percentage is 0.08%~0.12%, with Nano-meter SiO_2 is added after the solution in magnetic agitation 15~30 minutes in 800~1200 revs/min of revolving speed thereto2Microballoon, then magnetic Power is dispersed with stirring 30~60 minutes formation mixed solutions, SiO in mixed solution2Microspheres quality percentage composition be 0.15%~ 0.25%;Gained mixed solution is stood, is then centrifuged for isolated being adsorbed with Sn2+SiO2Microballoon (D);
Sn will be adsorbed with2+SiO2Microballoon (D) is scattered in deionized water or distilled water, is adsorbed with Sn2+SiO2Microballoon (D) The mass ratio of additional amount and deionized water or distilled water is 1:5, and AgNO is then added dropwise3Solution, wherein AgNO3In solution AgNO3Be adsorbed with Sn2+SiO2The mass ratio of the aqueous solution of microballoon (D) is 0.005:1~0.032:1, stirs 30~90 points Zhong Hou, then reducing agent is added dropwise, it is stirred for 1~3 hour after adding reducing agent, then, being centrifugally separating to obtain load has Ag The Nano-meter SiO_2 of grain2Microballoon, wherein the content of Ag particle accounts for the Nano-meter SiO_2 that load has Ag particle2The 5%~8% of microballoon gross mass;Institute Stating reducing agent is hydrazine, the additional amount and AgNO of reducing agent3Molar ratio be 1:1.4~1:2.0;
(3) by load Ag Nano-meter SiO_2 obtained above2Microballoon is scattered in alcohol solution, is then added into the solution and is contained perfluor The hydrolyzed silane solution of alkyl obtains antifouling antibacterial composite coating.
2. the preparation method of antifouling antibacterial composite coating according to claim 1, which is characterized in that molten in step (1) Liquid (A), mass ratio shared by water are 0.4%~2.6%, and mass ratio shared by ethyl orthosilicate is 1.8%~2.0%, and surplus is alcohol.
3. the preparation method of antifouling antibacterial composite coating according to claim 1 or 2, which is characterized in that in step (1), NH in alcohol ammonia solution (B)3Mass percentage is 3.1%~7.2%, and surplus is alcohol.
4. the preparation method of antifouling antibacterial composite coating according to claim 1, which is characterized in that in step (1), in room Under temperature, alcohol ammonia solution (B) is added in solution (A) and is given simultaneously and is stirred, mixing speed is 500~1000 turns/min;Alcohol ammonia Solution (B) is added completely into after solution (A) persistently stirs 30~120min again.
5. the preparation method of antifouling antibacterial composite coating according to claim 1 or 4, which is characterized in that in step (1), Alcohol ammonia solution (B) is added in solution (A) after persistently stirring, opening stands 24~72h and obtains solution (C), and solution (C) is centrifuged It separates and 1~3 hour dry at 100~180 DEG C to obtained solid product, obtains the Nano-meter SiO_2 that partial size is 10~75nm2It is micro- Ball.
6. the preparation method of antifouling antibacterial composite coating according to claim 1, which is characterized in that described in step (2) Acidic aqueous solution is hydrochloric acid deionized water solution, pH value 2.5.
7. the preparation method of antifouling antibacterial composite coating according to claim 1, which is characterized in that, will be upper in step (3) It states and carries the solution (I) that Ag nanosized SiO_2 microballoon is scattered in formation solid content 10%~20% in alcohol solution;By perfluoroalkyl silanes It is added in alcohol solution, and appropriate acid-catalyzed hydrolysis is added, obtain solution (II);By solution (I) with solution (II) according to certain Ratio mixing, obtain antifouling antibacterial composite coating;In this step, alcohol and water mixed volume ratio are 8:1~14 in alcohol solution: 1。
8. the preparation method of antifouling antibacterial composite coating according to claim 1 or claim 7, which is characterized in that in step (3), Perfluoroalkyl silanes and alcohol/aqueous solution are mixed, wherein mass ratio shared by perfluoroalkyl silanes is 1.5%~3%, and acid is then added Adjusting the solution ph is 4.5~6, is stirred 4~24 hours with 200~500 revs/min and obtains solution II;The perfluoroalkyl Silane structure formula are as follows:
It is 1~3, a is 0~2 that wherein m, which is 2~30, n,;It is hydrolyzable groups halogeno-group or alkane for perfluor carbochain or perfluoroether chain Oxygroup;For or alkoxy;The acid is the mixture of one of acetic acid, citric acid or both.
9. the preparation method of antifouling antibacterial composite coating according to claim 7, which is characterized in that solution (I) and solution (II) it mixes according to mass ratio 1:1~1:2, is stirred 0.5~4 hour with 200~500 revs/min.
10. the according to claim 1, preparation method of antifouling antibacterial composite coating described in 2,4,6,7 or 9, which is characterized in that institute The alcohol stated is one of ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol or wherein several mixtures.
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