CN102632022B - Preparation method of self-repairing transparent antibacterial coating - Google Patents
Preparation method of self-repairing transparent antibacterial coating Download PDFInfo
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Abstract
The invention belongs to the technical field of the preparation of self-repairing transparent antibacterial coatings and particularly relates to a method for preparing a transparent antibacterial coating with self-repairing capability by using a layer-by-layer assembly technology. The prepared coating can well inhibit Gram-positive and Gram-negative bacteria, has high transmittance in a visible region and can be simply repaired by immersing the coating in the water or spraying water on the coating due to the declined coating transparency by mechanical damage. By using the repairing method, the transparency of the coating firstly realizes complete self-repairing in the same region for many times. The preparation method of the self-repairing transparent antibacterial coating is simple with non-toxic and harmless raw materials used in the method, thus probably making some contribution to the researches with respect to material science, surface chemistry and the like; in addition, the self-repairing transparent antibacterial coating is expected to be widely used in the fields such as a touch human-computer interface (such as a touch display screen).
Description
Technical field
The invention belongs to the transparent antimicrobial coating preparing technical field of selfreparing, be specifically related to a kind of method of utilizing laminated assembling technology to prepare the transparent antimicrobial coating with self-reparing capability.
Background technology
Self-repair function can extend the service life of material effectively, reduce duplication of production and safeguard needed expense, and can improve material function security (Annu.Rev.Mater.Res.2010,40,179-211).Most of self-repair material can only be repaired its mechanical performance or its protective effect, and (Small 2007; 3; 926-943); only have a few materials can repair the function of himself; such as: the selfreparing of coating ultra-hydrophobicity (Angew.Chem.Int.Ed.2010,49,6129-6133) and the selfreparing (Adv.Mater.2012 of material electric conductivity; 24,398-401) etc.Transparent protective finish General Requirements has good transparency to base material, so suitable important of the transmitance of coating.A lot of transparent coatings are that preparation is on public touch display device, as touch display screen etc.Their can cause along with long use and mechanical damage the decline of transparency.To give these coatings higher security for the selfreparing of coating transparency.On the other hand, these clear coats are often touched by people.Touch can cause bacterium to remain in coating surface so frequently, so harm the people healthy (J.Appl.Microbiol.2010,109,1868-1874).So it is very necessary preparing transparent antimicrobial coating.And the transparent antimicrobial coating with self-reparing capability will have potential using value in fields such as touching man-machine interface.
A kind of method of the common foreign aid's of preparation type self-repair material be with renovation agent be loaded in nano particle (Nature2001,409,794-797) or the nanometer pipeline (Nat.Mater.2007,6,581-585) in and be embedded in advance material internal.When material was impaired under external force, nano particle or nanometer pipeline were destroyed under stress, and then renovation agent can discharge and fills up wound.The size of nano particle or nanometer pipeline is usually much larger than visible light wavelength, thereby this can cause scattering of light to affect the transparency of material.Moreover a lot of other factor, as wall thickness, the renovation agent of nano particle or nanometer pipeline and tight ness rating that refraction index matching degree, nano particle or the nanometer pipeline of material of main part are combined with material of main part, discharge tiny balloon after renovation agent, the surface topography after repairing etc., all can affect the transparency of self-repair material.Recently, the people such as Jackson (Adv.Funct.Mater.2011,21,4705-4711) utilize the renovation agent of refraction index coupling and the microcapsules of small scale to prepare transparent coatings, but the renovation agent quantity not sufficient of loading due to the microcapsules of small scale, so the part selfreparing that it can only realization transparency.If want to reach better repairing effect, can increase the yardstick of microcapsules, but the thing followed is the decline of the transparency of material own.So preparation foreign aid type selfreparing transparent material is very difficult.
(Science 2002 for the self-repair material of Intrinsical, 295,1698-1702), they do not comprise the large scales such as microcapsules and can cause the structure of light scattering and can cause the unmatched renovation agent of refraction index, so it is transparent that they are more easily made, and more likely realize the selfreparing of material transparency.In addition the self-repair material preparation method of Intrinsical simple, can realize the repeatedly advantage such as selfreparing of same position, so will be highly significant for the exploitation of the Intrinsical self-repair material of transparency selfreparing.But regrettably, at present also without any relevant report.
(Science 1997,227,1232-1237) for the advantages such as laminated assembling technology is a kind of important method for preparing coating material, and the cated composition of its tool, thickness and pattern height are controlled, the preparation of coating is not subjected to the substrate restriction.Recently, had the report that much utilizes laminated assembling technology to prepare foreign aid's type coatings (Adv.Mater.2008,20,2789-2794).We reported in work before a kind of method that utilization index increases laminated assembling technology and prepare the Intrinsical coatings (Angew.Chem.Int.Ed.2011,50,11378-11381).On the basis of working before, and be easy to the advantages such as regulation and control in conjunction with layer assembly coating structure and composition, we are expected to prepare the transparent antimicrobial coating of a kind of Intrinsical selfreparing.
Summary of the invention
The objective of the invention is based on laminated assembling technology, a kind of quick, simple, effective method for preparing the transparent antimicrobial coating with self-reparing capability is provided.
The prepared coating of the present invention all has fine inhibitory action to gram-negative, positive bacteria.This coating has high transmitance at visible region, and can realize its reparation by simply coating being immersed in water or to the coating water spray because mechanical damage causes the decline of coating transparency.Utilize this reparation means, the transparency of coating has realized the same area complete selfreparing repeatedly first.The preparation method of the transparent antimicrobial coating of this selfreparing is simple, advantages of nontoxic raw materials used is harmless, the proposition of believing this method will have to the research of the aspects such as material science, surface chemistry certain contribution, and the transparent antimicrobial coating of this selfreparing is expected to be widely used in fields such as touching man-machine interface (as touch display screen).
The method for preparing the transparent antimicrobial coating of selfreparing based on laminated assembling technology of the present invention, its step is as follows:
A. polycation and polyanion are dissolved in respectively solvent be made into concentration be 0.01～100mg/mL, pH value be 1～14 construct primitive solution;
B. the substrate after cleaning is immersed in polycation and constructed in primitive solution 1～40 minute, then substrate is taken out, the material of substrate surface physical absorption is removed in washing;
C. upper step substrate is immersed polyanion and constructed in primitive solution 1～40 minute, then substrate is taken out, the material of substrate surface physical absorption is removed in washing; Thereby complete the coating preparation of a deposition cycle;
D. repeating step B, C, complete the preparation of the coating of a plurality of deposition cycle in substrate, thereby obtain having the substrate of selfreparing clear coat;
E. antimicrobial is distributed in the surfactant solution that concentration is 0.01～1mol/L, the mol ratio of antiseptic and surfactant is 1: 300～1: 50, obtains antimicrobial after ultrasonic 5～200 minutes;
The substrate that F. will have a selfreparing clear coat is immersed in the antimicrobial of step 5～200 minutes, then substrate is taken out, and dries up with nitrogen after washing, thereby prepare the transparent antimicrobial coating of selfreparing in substrate.
In above-mentioned steps, the substrate that is used for constructing coating is various solid substrate commonly used, as quartz, optical glass, monocrystalline silicon, calcirm-fluoride, metal, plastics etc.Effect after various substrate cleanings are processed, wherein, quartz, optical glass, monocrystalline silicon boil till no longer produce bubble with the mixed solution of using again the concentrated sulfuric acid (mass fraction 95～98%) and hydrogen peroxide (volume ratio is 7: 3) after toluene, isopropyl alcohol, methyl alcohol ultrasonic cleaning successively; Metal, calcirm-fluoride substrate are cleaned with ethanol; Plastic-substrates successively with oxolane, methyl alcohol, water ultrasonic cleaning to remove surface impurity; Various substrates after above-mentioned processing are conducive to directly construct on its surface the layer assembly coating.
The polycation that the present invention uses is one or more in PAH (PAH), polyvinyl imines, gelatin, poly-tetrem thiazolinyl pyridine, polydiene propyl-dimethyl amine hydrochlorate, shitosan, polylysine, polyaniline; Polyanion is one or more in hyaluronic acid (HA), polyacrylic acid, kayexalate, sodium alginate, sulfonated polyether-ether-ketone, sulfonation glucan.
The solvent of dissolving polycation or polyanion is one or more in water, acetone, ethanol, DMF, dimethyl sulfoxide (DMSO), chloroform, carrene.
Polycation is constructed primitive and polyanion and is constructed primitive and mutually combine by active forces such as electrostatic force, hydrogen bond, coordinate bond, electric charge transfer, specific molecular identifications, and the consumption mol ratio of polycation and polyanion is 1: 10～10: 1.
Further, the concentration that polycation is constructed primitive solution is 0.1～50mg/mL, and the pH value is between 2～12; The concentration that polyanion is constructed primitive solution is 0.1～50mg/mL, and the pH value is 2～12, and the consumption mol ratio of polycation and polyanion is 1: 8～8: 1;
Again further, the concentration that polycation is constructed primitive solution is 1～10mg/mL, and the pH value is 7.5～12; The concentration that polyanion is constructed primitive solution is 1～10mg/mL, and the pH value is 2～6.5, and the consumption mol ratio of polycation and polyanion is 1: 5～5: 1;
Polycation in front in described various substrate Direct precipitation and without any need for finishing.In addition, polycation also contains in a large number functional groups freely, and (pH=1～14) with a large amount of positive charges, so just can carry out the deposition of next step polyanion easily by laminated assembling technology under pH value condition on a large scale.
Further, to construct at polycation the time that primitive solution and polyanion soak in constructing primitive solution be 5～20 minutes in substrate.
The surfactant that is dissolved in solvent can be because of the amphipathic micella that forms of himself when criticalization micellar concentration is above.Antiseptic namely can be loaded in the hydrophobic inner core of micella like this.And micellar surface can be loaded in clear coat with positive charge, thereby realizes the successful loading of antiseptic.
Further, the ultrasonic time in step e is 20～100 minutes, and the mol ratio of antiseptic and surfactant is 1: 200～1: 100, the concentration 0.01～0.5mol/L of surfactant solution; Soak time in step F is 20～150 minutes;
Surfactant is one or more in lauryl sodium sulfate (SDS), softex kw, benzyl cetyl chloride ammonium, neopelex.
Antiseptic is one or more in triclosan, metronidazole, Ceftriaxone Sodium, Cefazolin sodium, cephalosporin, silver nitrate, shitosan, poly-ε-lysine.
The anti-microbial property of transparent antimicrobial coating:
Escherichia coli Escherichia coli DH5a (E.coli) and bacillus subtilis Bacillus subtilis (B.subtils) are respectively as Gram-negative bacteria and the gram-positive bacteria antibacterial ability for detection of coating.Bacterium is placed in the culture medium (contain 50～200mg tryptone, 1～50mg yeast extract, 20～200mg sodium chloride and 1～20mL pH be 7.0 aqua sterilisa) of 37 ℃ and spends the night.Escherichia coli and bacillus subtilis are coated on solid agar medium (the solid agar medium is the prepared culture medium of agar that adds 1～3% quality in above-mentioned culture medium).Growth has the silicon base of antimicrobial coating to be placed on to be coated with on germy solid medium, to place under 37 ℃ 12～48 hours.
Transparent antimicrobial coating has high intensity in air (25 ℃, relative humidity approximately 25%), have mobility preferably in water, and the polyelectrolyte chain in coating just can move to impaired place in water like this, thereby reaches the effect of selfreparing.This intensity that has the transparent antimicrobial coating of intensity and self-reparing capability concurrently depends on its aerial high-modulus, and self-reparing capability depends on its low modulus in water.Its concrete damage and repair process are as follows: firmly swipe on coating with sand paper and destroy coating surface structure, cause serious light scattering, thereby the coating transparency is descended; Then coating is immersed in water or to coating and sprays water, the wound on coating will be repaired gradually, and the transparency of coating also is repaired gradually.
The present invention has developed a kind of utilization index growth laminated assembling technology and surfactant micella coats the method that antiseptic prepares transparent antibiotic coatings.Following characteristics has given this method very high practical value: (1) preparation coating laminated assembling technology used has large tracts of land non-planar substrate Direct precipitation and coating forms, the convenient controlled characteristics of structure, so this laminated assembling technology is particularly suitable for preparing the transparent antimicrobial coating of selfreparing; (2) only need simply coating to be immersed in water or to spray water to coating surface and can realize other reparation means such as heating, illumination are compared in the selfreparing completely of transparent antimicrobial coating transparency, water is undoubtedly a kind of reparation means of simple possible more; (3) this transparent antimicrobial coating can be realized repeatedly selfreparing of same position; (4) introducing of broad spectrum antimicrobicide makes this coating have good antibacterial effect, and the transparent antimicrobial coating of this selfreparing is expected to be applied to touch the fields such as man-machine interface.Profound level to transparent antimicrobial coating selfreparing mechanism is inquired into the concept that not only is conducive to promote selfreparing, more will play important effect aspect the exploitation of the new material with self-healing properties.
Description of drawings
The thickness of the PAH/HA coating of Fig. 1: embodiment 1 preparation and the graph of relation of number of deposition cycles;
Fig. 2: (PAH/HA) * 30.5 coatings are loaded the corresponding uv-visible absorption spectra figure of triclosan different time,
Illustration is that (PAH/HA) * 30.5 coatings are loaded the time dependent loading curve of triclosan molecule, corresponding embodiment 2;
Fig. 3: (PAH/HA) * 30.5 coatings that are mounted with triclosan discharge the time dependent release profiles of triclosan molecule, corresponding embodiment 3 in water;
Fig. 4: (PAH/HA) * 30.5 coatings that are mounted with triclosan are to (a) Escherichia coli and (b) the antibacterial ability figure of bacillus subtilis, corresponding embodiment 3;
Fig. 5: (a-c) be digital photograph, (a) be mounted with (PAH/HA) * 30.5 coatings of triclosan, (b) (PAH/HA) * 30.5 coatings that are mounted with triclosan (c) are mounted with (PAH/HA) * 30.5 coatings of triclosan through after damage, repairing through after damaging; (d-f) be atomic force microscopy, (d) be mounted with (PAH/HA) * 30.5 coatings of triclosan, (e) be mounted with (PAH/HA) * 30.5 coatings of triclosan through after damaging, (f) (PAH/HA) * 30.5 coatings that are mounted with triclosan are through after damage, repairing, corresponding embodiment 4;
Fig. 6: ultraviolet-visible sees through spectrogram, (a) (PAH/HA) * 30.5 coatings, (b) (PAH/HA) after * 30.5 coatings are loaded triclosans, (c) be mounted with (PAH/HA) * 30.5 coatings of triclosan through after damaging, (d) (PAH/HA) * 30.5 coatings that are mounted with triclosan are through after damage, repairing, corresponding embodiment 4;
Fig. 7: optical microscope photograph, (a) be mounted with (PAH/HA) * 30.5 coatings of triclosan, (b) impaired (PAH/HA) * 30.5 coatings that are mounted with triclosan, impaired (PAH/HA) * 30.5 coatings that are mounted with triclosan are soaked 10 seconds (c), 1 minute (d), 5 minutes (e), 10 minutes (f), 30 minutes (g) in water after, corresponding embodiment 4;
Fig. 8: (PAH/HA) * 5 damages of 30.5 coating experience and the corresponding ultraviolet-visible of repair process that are mounted with triclosan see through spectrum at the transmitance value at 550nm place, corresponding embodiment 4;
Fig. 9: (PAH/HA) * 30.5 coatings are loaded the mechanical performance of triclosan front and back, (a, b) (PAH/HA) * 30.5 coatings loads the relation curve that the Young's modulus (a) under dry state and hardness (b) change with compression distance before and after triclosans; (c) (PAH/HA) * 30.5 coatings are loaded before and after triclosans the storage modulus in water and loss modulus with the relation curve of change of frequency, wherein, (A, B) (PAH/HA) * 30.5 coatings are loaded before triclosans (B) storage modulus in water after (A), (C, D) (PAH/HA) * 30.5 coatings loads before triclosans (D) loss modulus in water after (C); (d) (PAH/HA) * 30.5 coatings are loaded the fissipation factor of triclosan front and back in water with the relation curve of change of frequency, corresponding embodiment 5.
The specific embodiment
Below further illustrate concrete enforcement of the present invention and result by some examples, rather than to limit the present invention with these examples.
Embodiment 1: the preparation of transparent PAH/HA coating
Quartz substrate after processing is immersed in PAH (2mg/mL, the pH=10) aqueous solution 15 minutes, takes out the substrate after washing, then be immersed in HA (2mg/mL, the pH=3) aqueous solution 15 minutes, take out the substrate after washing.Wherein, the pH value of PAH and the HA aqueous solution all utilizes concentration to regulate for the 1mol/L sodium hydrate aqueous solution for aqueous hydrochloric acid solution and the concentration of 1mol/L.
Repeat above-mentioned steps 30.5 times (being that last one deck is the PAH layer), namely obtain transparent PAH/HA coating.Fig. 1 utilizes the coating layer thickness of surface sweeping electron microscope tracking and monitoring with the relation curve of number of deposition cycles variation.Illustrated that this coatings growth is typical exponential increase situation, namely along with the increase of number of deposition cycles, the thickness of coating increases fast.30.5 the thickness of this coating of cycle is about 17.8 ± 0.5 microns.
Embodiment 2: the preparation of transparent antimicrobial coating
(PAH/HA) * 30.5 coatings on public display device surface, must be faced various bacteriums and virus as protective finish preparation, are chosen as antiseptic and are introduced into (PAH/HA) * 30.5 coatings so have the triclosan molecule of broad-spectrum antimicrobial effect.The triclosan molecule is hydrophobic molecule, be difficult to be introduced directly in hydrophilic (PAH/HA) * 30.5 coatings by common method, so adopt the method that surfactant micella coats that hydrophobic triclosan molecule is introduced in (PAH/HA) * 30.5 coatings.
In this example, at first the dichloromethane solution (0.15mol/L) with the 0.2mL triclosan is added drop-wise in the aqueous solution (0.1mol/L) of 40mL SDS, ultrasonic 1 hour.The triclosan molecule can be covered by in the hydrophobic internal cavities of SDS micella due to hydrophobic interaction.Then (PAH/HA) * 30.5 coatings are immersed in the SDS micellar solution that is mounted with the triclosan molecule, the SDS micella that is mounted with triclosan will be loaded into by electrostatic interaction (PAH/HA) * 30.5 coatings.We adopt ultraviolet visible spectrometry to characterize this loading process.As shown in Figure 2, in coating, the triclosan molecule is being mounted with the growth of soak time in the SDS micellar solution of triclosan and is increasing along with coating at the characteristic absorption peak value at 281nm place.Through the immersion of about 2 hours, the SDS micella load that is mounted with in a large number triclosan entered in coating.This proof triclosan molecule successfully has been incorporated in (PAH/HA) * 30.5 coatings by the method that surfactant coats.Notably that (PAH/HA) * 30.5 coatings of having loaded triclosan are still optically transparent in the visual field.
Embodiment 3: the antibacterial ability of transparent antimicrobial coating
The delivery of antimicrobials that continues from coating effectively anti-bacteria growth and safeguard the mankind's health, so delivery of antimicrobials is very important for a long time.Be loaded in (PAH/HA) * 30.5 coatings the release profiles of triclosan molecule in water as shown in Figure 3.What the triclosan molecule can continue is released in water, and in initial 12 hours, the rate of release of triclosan molecule is than faster, and this is the release dynamics that typically extends influence.After release in, the rate of release of triclosan molecule in water slows down, whole dispose procedure can continue 20 days.And when the transparent antimicrobial coating of practical application, it generally is in and has in certain relative humidity air ambient, so it can guarantee the longer time antibacterial effect, can adapt to the requirement of practical application fully.Calibration curve (Y=0.0121*X-0.0035, r according to the triclosan aqueous solution under room temperature
2=0.994) calculate: the useful load of triclosan molecule in (PAH/HA) * 30.5 coatings is 6.1 ± 0.7 μ g/cm
2
Adopt through certain Kirby-Bauer that revises test to verify (PAH/HA) * 30.5 coatings that are mounted with the triclosan molecule bacteriostasis (Am.J.Clin.Pathol.1966,45,493-496).We have the substrate of (PAH/HA) * 30.5 coatings that are mounted with the triclosan molecule to be placed on respectively on the agar plate that scribbles Escherichia coli and bacillus subtilis with long, place 24 hours for 37 ℃.As shown in Figure 4, no matter be to Escherichia coli or to bacillus subtilis, get in (PAH/HA) * 30.5 coatings that are mounted with the triclosan molecule and produced obvious antibacterial ring on every side.This explanation is mounted with triclosan molecule (PAH/HA) * 30.5 coatings all has good antibacterial effect to Gram-negative bacteria and gram-positive bacteria.And the coating of not loading triclosan is to bacterium unrestraint effect.
Embodiment 4: the self-reparing capability of transparent antimicrobial coating
The optical transmittance of transparent antimicrobial coating is very important.In case coating wrecks, its transmitance can produce irreversible decline significantly, and this will affect the use of transparent antimicrobial coating greatly.In order to give transparent antimicrobial coating with long-acting durability, the present invention is devoted to the selfreparing of its transmitance.We utilize 1500 purpose Sandpaperings to make the cut of coating surface.Damage and the process of repairing characterize by digital photo, AFM and ultraviolet visible spectrometry respectively.As shown in Figure 5, (PAH/HA) * 30.5 coating surfaces that are mounted with triclosan of preparation are very smooth, and have good transparency.When utilizing sand paper firmly to rub after this coating surface, smooth coating structure is destroyed, and the transparency of coating descends.Utilizing AFM and line thereof to sweep analysis obtains: the width of cut is that 4.3 ± 1.0 μ m degree of depth are 1.3 ± 0.4 μ m.Impaired coating was immersed in water after 30 minutes, and the cut of coating surface is repaired, coat resuming original transparency.
Fig. 6 has characterized (PAH/HA) * 30.5 coatings and has loaded triclosan and be mounted with (PAH/HA) * 30.5 coating damages of triclosan and the transparency after reparation.Can see, after loading triclosan, (PAH/HA) * 30.5 coatings have in the visual field～85% transmitance; After damage, the transmitance of coating drops to below 40%; After the reparation that was immersed in water in 30 minutes, coating has been recovered again the transmitance of visual field～85%.
The selfreparing degree of transparent antimicrobial coating is to depend on soak time in water.Want to carry out selfreparing thoroughly and usually coating need to be immersed in water 30 minutes.As shown in Figure 7a, unmarred coating is comparatively smooth, and through after the damage of sand paper, coating surface becomes very coarse (Fig. 7 b).When soak 10 seconds in water after, the cut of coating surface has the trend of reparation (Fig. 7 c).Along with the growth of soak time, the cut of coating surface becomes gradually not obvious (Fig. 7 d-f).After 30 minutes, the cut of coating surface has obtained repairing completely in being immersed in water, and coating has been recovered again even curface pattern (Fig. 7 g).This has proved by being immersed in water 30 minutes, can realize the selfreparing completely to transparent antimicrobial coating.
This transparent antimicrobial coating is a kind of Intrinsical self-repair material, so it has the repeatedly ability of selfreparing of same position.We adopt ultraviolet visible spectrometry to follow the tracks of the situation of change of coating transmitance at 550nm place in 5 damage-repair processes, list in Fig. 8.Unmarred coating has at the 550nm place～86% transmitance, and the transmitance of the coating after damage is lower than 42%, and the transmitance after each the reparation all can return to more than 85%.This proof, this transparent antimicrobial coating can be realized repeatedly selfreparing of same position.
Embodiment 5: the mechanical performance of transparent antimicrobial coating and repair mechanisms
We adopt nanometer mechanics test macro (Agilent Technologies Nano Indenter G200System) that the mechanical property of transparent antibiotic coatings is analyzed.Utilize " G-series CSM Standard Hardness; Modulus; and Tip Cal " method that Young's modulus and the hardness that (PAH/HA) * 30.5 coatings on silicon base load before and after triclosans that is grown in of (30 ℃, 18% relative humidity) under dry state is measured.As shown in Fig. 9 a, Young's modulus has occurred an of short duration platform with the curve 150nm of compression distance to the 300nm place.The mean value of the Young's modulus on this platform just can be considered to the intrinsic Young's modulus of material.More than 300nm, Young's modulus constantly increases along with the increase of compression distance, and this is in hard suprabasil substrate effect due to soft coating.For the hardness of the coating shown in Fig. 9 b curve with change in depth, the mean value of the hardness at 500～700nm place can be thought the intrinsic hardness of material.
Under table 1, dry state, (PAH/HA) * 30.5 coatings of (30 ℃, 18% relative humidity) are loaded the mechanical performance of triclosan front and back.
(PAH/HA) during before and after * 30.5 coatings loading triclosans, the intrinsic Young's modulus under dry state and intrinsic hardness number are listed in table 1.Can see, after loading triclosan, the Young's modulus of coating and hardness number all have small decline.Be notably, modulus and the hardness of the transparent antimicrobial coating of selfreparing under dry state is respectively 8.9 ± 1.2GPa and 0.41 ± 0.05GPa, and this proves that it has good mechanical performance under dry state, can adapt to the requirement of practical application fully.
Table 2,30.5 coatings of (PAH/HA) * in water are loaded the mechanical performance (frequency is under the 1Hz condition) before and after triclosan.
Next, utilize " G-Series XP CSM Flat Punch Complex Modulus " method that storage modulus, loss modulus and the fissipation factor that (PAH/HA) * 30.5 coatings on silicon base load before and after triclosans that be grown in water measured.As shown in Fig. 9 c and d, the storage modulus of coating, loss modulus and fissipation factor all change with the variation of frequency.And only coating need to be immersed in static water when our selfreparing, so we mainly study storage modulus, loss modulus and fissipation factor in the lower coating of lower frequency (1Hz), be listed in table 2.Can find out, after coating was loaded triclosan, modulus had certain decline, and this is because the introducing of the triclosan molecule that the SDS micella coats can destroy the crosslinked structure of PAH/HA coating static to a certain extent, thereby causes its mechanical performance that a little decline is arranged.The modulus of coating during the contrast dry state, coating has low-down modulus in water, and at this moment, coating has good flexibility, and the molecule segment in coating can carry out migration to a certain degree, thereby repairs cut.We notice, the fissipation factor of coating in water the time be close to 1, and the viscoplasticity of this explanation coating in water the time is close to gel.At present, (Macromolecules 2010,43,1191-1194) for the gel that has had a lot of reports to study to have self-reparing capability.If transparent antimicrobial coating in water is thought a kind of material that is similar to gel, its repair mechanisms also just have been understood that so.On the one hand, water has given transparent antimicrobial coating suitable viscoplasticity, and making not, the strand of damaged portion can move to damaged part; On the other hand, in coating, reversible ionic bond provides the coating binding site of Cheng Jian again, thus the coating after firm the reparation.
Claims (3)
1. method for preparing the transparent antimicrobial coating of selfreparing based on laminated assembling technology, its step is as follows:
A. polycation and polyanion are dissolved in respectively solvent be made into concentration be 0.01～100mg/mL, pH value be 1～14 construct primitive solution;
B. the substrate after cleaning is immersed in polycation and constructed in primitive solution 1～40 minute, then substrate is taken out, the material of substrate surface physical absorption is removed in washing;
C. upper step substrate is immersed polyanion and constructed in primitive solution 1～40 minute, then substrate is taken out, the material of substrate surface physical absorption is removed in washing; Thereby complete the coating preparation of a deposition cycle;
D. repeating step B, C, complete the preparation of the coating of a plurality of deposition cycle in substrate, thereby obtain having the substrate of selfreparing clear coat;
E. antimicrobial is distributed in the surfactant solution that concentration is 0.01～1mol/L, the mol ratio of antiseptic and surfactant is 1:300～1:50, obtains antimicrobial after ultrasonic 5～200 minutes;
The substrate that F. will have a selfreparing clear coat is immersed in the antimicrobial of step 5～200 minutes, then substrate is taken out, and dries up with nitrogen after washing, thereby prepare the transparent antimicrobial coating of selfreparing in substrate;
Wherein, polycation is one or more in PAH, polyvinyl imines, gelatin, poly-tetrem thiazolinyl pyridine, polydiene propyl-dimethyl amine hydrochlorate, shitosan, polylysine, polyaniline; Polyanion is one or more in hyaluronic acid, polyacrylic acid, sodium alginate, kayexalate, sulfonated polyether-ether-ketone, sulfonation glucan; The consumption mol ratio of polycation and polyanion is 1:10～10:1; Antiseptic is one or more in triclosan, metronidazole, Ceftriaxone Sodium, Cefazolin sodium, cephalosporin, silver nitrate, shitosan, poly-ε-lysine; Surfactant is one or more in lauryl sodium sulfate, softex kw, benzyl cetyl chloride ammonium, neopelex; Solvent is one or more in water, acetone, ethanol, DMF, dimethyl sulfoxide (DMSO), chloroform, carrene; Substrate is quartz, optical glass, monocrystalline silicon, calcirm-fluoride, metal or plastics.
2. a kind of method for preparing the transparent antimicrobial coating of selfreparing based on laminated assembling technology as claimed in claim 1, it is characterized in that: the concentration that polycation is constructed primitive solution is 0.1～50mg/mL, and the pH value is between 2～12; The concentration that polyanion is constructed primitive solution is 0.1～50mg/mL, and the pH value is 2～12, and the consumption mol ratio of polycation and polyanion is 1:8～8:1.
3. a kind of method for preparing the transparent antimicrobial coating of selfreparing based on laminated assembling technology as claimed in claim 2, it is characterized in that: the concentration that polycation is constructed primitive solution is 1～10mg/mL, and the pH value is 7.5～12; The concentration that polyanion is constructed primitive solution is 1～10mg/mL, and the pH value is 2～6.5, and the consumption mol ratio of polycation and polyanion is 1:5～5:1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN104387832B (en) * | 2014-09-29 | 2016-06-08 | 北京师范大学 | A kind of compound fungistatic coating preparation method being loaded with small-molecule substance |
| WO2018183060A1 (en) * | 2017-03-28 | 2018-10-04 | The Texas A&M University System | Coatings for materials |
| CN107375995A (en) * | 2017-07-21 | 2017-11-24 | 临沂市人民医院 | A kind of preparation method based on layer assembly function selfreparing aquogel type dressing materials |
| CN107502133B (en) * | 2017-08-11 | 2019-04-30 | 北京师范大学 | The corrosion-inhibiting coating and its preparation method and application for having self-reparing capability |
| CN108192126B (en) * | 2018-01-17 | 2020-12-04 | 长沙理工大学 | Preparation method of antibacterial coating based on polyimidazolium salt |
| CN109880139A (en) * | 2019-01-21 | 2019-06-14 | 桐城市中汇塑业有限公司 | A kind of PE film with gel layer |
| CN110054984B (en) * | 2019-05-08 | 2021-03-05 | 常州大学 | Preparation method of covalent cross-linking self-healing antibacterial coating with stable structure |
| CN110170429A (en) * | 2019-05-20 | 2019-08-27 | 东南大学 | A kind of preparation method of iron-based bottom adherency enhancing coatings |
| CN111558089B (en) * | 2020-05-18 | 2021-01-29 | 临沂市人民医院 | Multifunctional biomedical material and preparation and application thereof |
| CN113583526A (en) * | 2021-07-26 | 2021-11-02 | 畅的新材料科技（上海）有限公司 | Stain-resistant self-repairing coating and preparation method thereof |
| CN114773623A (en) * | 2022-03-03 | 2022-07-22 | 杭州爱卓科技有限公司 | Use of reversible gel materials as starting materials for the production of medical models |
| CN114989720B (en) * | 2022-05-31 | 2023-06-16 | 华中科技大学 | Self-cleaning, anti-fog, antibacterial and self-repairing multifunctional coating and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101934202A (en) * | 2010-08-17 | 2011-01-05 | 浙江大学 | Method for preparing antimicrobial polymer separation membrane |
| CN102319662A (en) * | 2011-09-26 | 2012-01-18 | 吉林大学 | Method for preparing self-repairing polyelectrolyte coating based on layer-by-layer assembly technology |
| TW201204562A (en) * | 2010-07-30 | 2012-02-01 | Univ Nat Formosa | Mixed self-assembly molecular structure capable of reducing spore germination rate and preparation method thereof |
-
2012
- 2012-05-01 CN CN 201210132441 patent/CN102632022B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201204562A (en) * | 2010-07-30 | 2012-02-01 | Univ Nat Formosa | Mixed self-assembly molecular structure capable of reducing spore germination rate and preparation method thereof |
| CN101934202A (en) * | 2010-08-17 | 2011-01-05 | 浙江大学 | Method for preparing antimicrobial polymer separation membrane |
| CN102319662A (en) * | 2011-09-26 | 2012-01-18 | 吉林大学 | Method for preparing self-repairing polyelectrolyte coating based on layer-by-layer assembly technology |
Non-Patent Citations (2)
| Title |
|---|
| 《壳聚糖及其表面活性剂复合物的抗菌性与抗菌机理的研究》;刘慧;《中国优秀硕士学位论文全文数据库》;20041231(第4期);第5章第2.1-2.3节,3.3节 * |
| 刘慧.《壳聚糖及其表面活性剂复合物的抗菌性与抗菌机理的研究》.《中国优秀硕士学位论文全文数据库》.2004,(第4期),第5章第2.1-2.3节,3.3节. |
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