CN102632022A - 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 transparent antimicrobial coating with self-reparing capability.
Background technology
Self-repair function can prolong 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); Have only 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.The general requirement of transparent protective coating has good transparency to base material, so suitable important of the transmitance of coating.A lot of transparent coatings are to be prepared on the public touch display device, like touch display screen etc.Their can cause the decline of transparency along with long use and mechanical damage.To give these coatings higher security to the selfreparing of coating transparency.On the other hand, these clear coats are often touched by people.Frequent like this touch can cause bacterium to remain in coating surface, 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 into material internal in advance.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 wavelength of visible light, thereby this can cause scattering of light to influence the transparency of material.Moreover a lot of other factor; The tight ness rating that combines with material of main part like the wall thickness of nano particle or nanometer pipeline, renovation agent and refraction index matching degree, nano particle or the nanometer pipeline of material of main part, discharge tiny balloon behind the renovation agent, the surface topography after repairing etc., all can influence the transparency of self-repair material.Recently; 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 selfreparing coating, but because the renovation agent quantity not sufficient that the microcapsules of small scale load, 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 large scales such as microcapsules can cause the structure of light scattering and can cause the unmatched renovation agent of refraction index, so that they are processed more easily is transparent, and more likely realizes the selfreparing of material transparency.In addition the self-repair material preparation method of Intrinsical simple, can realize repeatedly advantage such as selfreparing of same position, so will be highly significant to the exploitation of the Intrinsical self-repair material of transparency selfreparing.But regrettably, also has no relevant report at present.
Laminated assembling technology is a kind of important method for preparing coating material, and composition, thickness and the pattern height preparation controlled, coating that it has a coating does not receive advantages such as substrate restriction, and (Science 1997,227,1232-1237).Recently, had the report that much utilizes laminated assembling technology to prepare foreign aid's type selfreparing coating (Adv.Mater.2008,20,2789-2794).We before work in reported the method that a kind of utilization index increases laminated assembling technology and prepare Intrinsical selfreparing coating (Angew.Chem.Int.Ed.2011,50,11378-11381).On the basis of work before, and combine layer assembly coating structure and composition to be easy to advantages such as regulation and control, 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, provide transparent antimicrobial coating that a kind of preparation has self-reparing capability fast, simple, effective method.
Coatings prepared 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 through simply coating being immersed in the 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; Used advantages of nontoxic raw materials is harmless; The proposition of believing this method will have certain contribution to the research of aspects such as material science, surface chemistry, and the transparent antimicrobial coating of this selfreparing is expected to be widely used in touch man-machine interface fields such as (like touch display screens).
Of the present inventionly prepare the method for the transparent antimicrobial coating of selfreparing based on laminated assembling technology, its step is following:
A. with polycation and polyanion be 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 the clean is immersed in polycation and constructed in the primitive solution 1～40 minute, then substrate is taken out, the material of substrate surface physical absorption is removed in washing;
C. will go up the step substrate and immerse polyanion and constructed in the primitive solution 1～40 minute, and then substrate taken out, the material of substrate surface physical absorption is removed in washing; Thereby accomplish the production of coatings of a deposition cycle;
D. repeating step B, C accomplish 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 the washing back dries up with nitrogen, thereby in substrate, prepares the transparent antimicrobial coating of selfreparing.
In the above-mentioned steps, the substrate that is used for constructing coating is various solid substrate commonly used, like quartz, optical glass, monocrystalline silicon, calcirm-fluoride, metal, plastics etc.Act on after the various substrate clean; Wherein, quartz, optical glass, monocrystalline silicon boil till no longer produce bubble with the mixed solution of using the concentrated sulfuric acid (mass fraction 95～98%) and hydrogen peroxide solution (volume ratio is 7: 3) after toluene, isopropyl alcohol, the methyl alcohol ultrasonic cleaning again 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 help directly constructing on its surface the layer assembly coating.
The polycation that the present invention uses as PAH hydrochloride (PAH), polyvinyl imines, gelatin, gather tetrem thiazolinyl pyridine, polydiene propyl-dimethyl amine hydrochlorate, shitosan, gather in L-lysine, the polyaniline one or more; Polyanion is one or more in hyaluronic acid (HA), polyacrylic acid, kayexalate, sodium alginate, sulfonated polyether-ether-ketone, the sulfonation glucan.
The solvent of dissolving polycation or polyanion is water, acetone, ethanol, N, one or more in dinethylformamide, dimethyl sulfoxide (DMSO), chloroform, the carrene.
Polycation is constructed primitive and polyanion and is constructed primitive and mutually combine through 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 can described in front various substrates on directly deposition and without any need for finishing.In addition, polycation also contains in a large number functional groups freely, and (pH=1～14) have a large amount of positive charges under the pH value condition on a large scale, so just can carry out the deposition of next step polyanion easily through laminated assembling technology.
Further, substrate is constructed primitive solution and polyanion at polycation to construct the time of soaking in the primitive solution is 5～20 minutes.
The surfactant that is dissolved in the solvent can be because of the amphipathic micella that forms of himself when criticalization micellar concentration is above.Antiseptic promptly can be loaded in the hydrophobic inner core of micella like this.And micellar surface has positive charge, can be loaded in the clear coat, thus the successful loading of realization antiseptic.
Further, the ultrasonic time in the 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 the step F is 20～150 minutes;
Surfactant is one or more in lauryl sodium sulfate (SDS), softex kw, benzyl cetyl chloride ammonium, the neopelex.
Antiseptic is triclosan, metronidazole, Ceftriaxone Sodium, Cefazolin sodium, cephalosporin, silver nitrate, shitosan, gather in ε-lysine one or more.
The anti-microbial property of transparent antimicrobial coating:
Escherichia coli Escherichia coli DH5a (E.coli) and bacillus subtilis Bacillus subtilis (B.subtils) are used to detect the antibacterial ability of coating respectively as Gram-negative bacteria and gram-positive bacteria.Bacterium is placed in 37 ℃ the culture medium (contain 50～200mg tryptone, 1～50mg yeast extract, 20～200mg sodium chloride and 1～20mL pH be 7.0 aqua sterilisa) and spends the night.Escherichia coli and bacillus subtilis are coated on the solid agar medium (the solid agar medium is the prepared culture medium of agar that in above-mentioned culture medium, adds 1～3% quality).Growth had the silicon base of antimicrobial coating to be placed on the solid medium that scribbles bacterium, 37 ℃ of held 12～48 hours.
Transparent antimicrobial coating has high intensity in air (25 ℃, relative humidity about 25%), in water, then have good mobility, and the polyelectrolyte chain in the coating just can be moved 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 following: 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 the water or to coating and sprays water, the wound on the coating will be repaired gradually, and the transparency of coating is also 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 selfreparing coating.Following characteristics have given this method very high practical value: the used laminated assembling technology of (1) preparation coating has the advantages that the large tracts of land non-planar substrate directly deposits and coating is formed, structure is conveniently controlled, 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 the water or to the coating surface water spray 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 fields such as man-machine interface.Profound level to transparent antimicrobial coating selfreparing mechanism is inquired into the notion that not only helps promoting 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 pairing 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, (PAH/HA) * 30.5 coatings that (b) are mounted with triclosan are through after damaging, and (PAH/HA) * 30.5 coatings that (c) are mounted with triclosan are through after damage, repairing; (d-f) be the AFM photo; (d) be mounted with (PAH/HA) * 30.5 coatings of triclosan; (e) (PAH/HA) * 30.5 coatings that are mounted with triclosan through damage after, (PAH/HA) * 30.5 coatings that (f) 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 triclosan; (c) (PAH/HA) * 30.5 coatings that are mounted with triclosan through damage after, (PAH/HA) * 30.5 coatings that (d) 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: 5 damages of (PAH/HA) * 30.5 coatings experience and the pairing ultraviolet-visible of repair process that are mounted with triclosan see through the transmitance value of spectrum at the 550nm place, corresponding embodiment 4;
Fig. 9: (PAH/HA) * 30.5 coatings are loaded the mechanical performance of triclosan front and back, (a, the relation curve that b) Young's modulus (a) under dry state and hardness (b) change with compression distance before and after (PAH/HA) * 30.5 coatings loading triclosan; (c) (PAH/HA) * 30.5 coatings are loaded before and after the triclosan 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 (A) back (B) storage modulus in water before the triclosan, (C, D) (PAH/HA) * 30.5 coatings are loaded (C) back (D) loss modulus in water before the triclosan; (d) (PAH/HA) * 30.5 coatings are loaded the relation curve of the fissipation factor of triclosan front and back in water with change of frequency, corresponding embodiment 5.
The specific embodiment
Below come further to illustrate practical implementation of the present invention and result through some instances, rather than to limit the present invention with these instances.
Embodiment 1: the preparation of transparent PAH/HA coating
With the quartz substrate after handling be immersed in PAH (2mg/mL, pH=10) in the aqueous solution 15 minutes, take out the substrate after washing, (2mg/mL pH=3) in the aqueous solution 15 minutes, takes out the substrate after washing to be immersed in HA again.Wherein, PAH and HA pH value of aqueous solution all utilize 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), promptly obtain transparent PAH/HA coating.Fig. 1 utilizes the relation curve of the coating layer thickness of surface sweeping electron microscope tracking and monitoring with the number of deposition cycles variation.Explained that this is coated with layer growth and is typical exponential increase situation, promptly 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 are prepared in public display device surface as protective finish, must face various bacteriums and virus, 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 a hydrophobic molecule, is difficult to be introduced directly in hydrophilic (PAH/HA) * 30.5 coatings through common method, so the method that adopts surfactant micella to coat is introduced hydrophobic triclosan molecule 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 owing to hydrophobic interaction is covered by in the hydrophobic internal cavities of SDS micella.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 (PAH/HA) * 30.5 coatings through electrostatic interaction.We adopt ultraviolet visible spectrometry to characterize this loading process.As shown in Figure 2, the triclosan molecule is being mounted with the growth of soak time in the SDS micellar solution of triclosan and is increasing in the coating along with coating at the characteristic absorption peak value at 281nm place.Through about 2 hours immersion, the SDS micella load that is mounted with triclosan in a large number gets in the coating.This proof triclosan molecule successfully has been incorporated in (PAH/HA) * 30.5 coatings through the method that surfactant coats.Notably be that (PAH/HA) * 30.5 coatings of having loaded triclosan still are optically transparent in the visual field.
Embodiment 3: the antibacterial ability of transparent antimicrobial coating
The delivery of antimicrobials that from coating, continues can suppress the growth of bacterium effectively and safeguard human beings'health, so delivery of antimicrobials is very important for a long time.The release profiles of triclosan molecule in water that is loaded in (PAH/HA) * 30.5 coatings is as shown in Figure 3.What the triclosan molecule can continue is released in the 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 requirement of actual application fully.Calibration curve (Y=0.0121*X-0.0035, r according to the triclosan aqueous solution under the 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 the bacteriostasis of verifying (PAH/HA) * 30.5 coatings that are mounted with the triclosan molecule (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 tangible 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 crucial.In case coating wrecks, its transmitance can produce irreversible significantly decline, and this will influence 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 through 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 behind 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 the water after 30 minutes, and the cut of coating surface is repaired, and coating has been recovered 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 the reparation.Can see, load triclosan after, (PAH/HA) * 30.5 coatings have in the visual field～85% transmitance; After the damage, the transmitance of coating drops to below 40%; After the reparation that was immersed in the water in 30 minutes, coating has been recovered the transmitance of visual field～85% again.
The selfreparing degree of transparent antimicrobial coating is to depend on soak time in water.Want to carry out selfreparing completely and need coating be immersed in the water 30 minutes usually.Shown in Fig. 7 a, unmarred coating is comparatively smooth, and through after the damage of sand paper, coating surface becomes very coarse (Fig. 7 b).After in water, soaking 10 seconds, 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 even curface pattern (Fig. 7 g) again.This has proved through being immersed in the 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 among Fig. 8.Unmarred coating has at the 550nm place～86% transmitance, and the transmitance of the coating after the 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 selfreparing coating is analyzed." G-series CSM Standard Hardness; Modulus; the and Tip Cal " method of utilization is measured the Young's modulus and the hardness that are grown in (PAH/HA) * 30.5 coatings loading triclosan front and back on the silicon base of (30 ℃, 18% relative humidity) under the dry state.Shown in Fig. 9 a, Young's modulus an of short duration platform occurred 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, this be since soft coating in hard suprabasil substrate effect.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.
(PAH/HA) * 30.5 coatings of (30 ℃, 18% relative humidity) are loaded the mechanical performance of triclosan front and back under table 1, the dry state.
(PAH/HA) intrinsic Young's modulus and the intrinsic hardness number under dry state listed in the table 1 before and after the * 30.5 coatings loading triclosan.Can see that behind the loading triclosan, the Young's modulus of coating and hardness number all have small decline.Notably be, 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 requirement of actual application fully.
Table 2, (PAH/HA) * 30.5 coatings in water are loaded the mechanical performance (frequency is under the 1Hz condition) before and after the triclosan.
Next, utilize " G-Series XP CSM Flat Punch Complex Modulus " method that the storage modulus, loss modulus and the fissipation factor that are grown in (PAH/HA) * 30.5 coatings loading triclosan front and back on the silicon base in water are measured.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 need coating be immersed in the static water our selfreparing the time, so we mainly study in lower frequency (1Hz) storage modulus, loss modulus and the fissipation factor of coating down, be listed in the table 2.Can find out that after coating was loaded triclosan, modulus had certain decline, 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 the coating can carry out migration to a certain degree, thereby repairs cut.We notice, the fissipation factor of coating in water the time approaches 1, and the viscoplasticity of this explanation coating in water the time approaches 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 think a kind of material that is similar to gel to transparent antimicrobial coating in water, its repair mechanisms also just have been understood that so.On the one hand, water has given transparent antimicrobial coating suitable viscoplasticity, makes not the strand of damaged portion can move to damaged part; On the other hand, reversible ionic bond then provides the coating binding site of Cheng Jian again in the coating, thus the coating after firm the reparation.
Claims (10)
1. one kind prepares the method for the transparent antimicrobial coating of selfreparing based on laminated assembling technology, and its step is following:
A. with polycation and polyanion be 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 the clean is immersed in polycation and constructed in the primitive solution 1～40 minute, then substrate is taken out, the material of substrate surface physical absorption is removed in washing;
C. will go up the step substrate and immerse polyanion and constructed in the primitive solution 1～40 minute, and then substrate taken out, the material of substrate surface physical absorption is removed in washing; Thereby accomplish the production of coatings of a deposition cycle;
D. repeating step B, C accomplish 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 the washing back dries up with nitrogen, thereby in substrate, prepares the transparent antimicrobial coating of selfreparing.
2. a kind ofly according to claim 1 prepare the method for the transparent antimicrobial coating of selfreparing based on laminated assembling technology, it is characterized in that: polycation is PAH hydrochloride, polyvinyl imines, gelatin, gather tetrem thiazolinyl pyridine, polydiene propyl-dimethyl amine hydrochlorate, shitosan, gather in L-lysine, the polyaniline one or more.
3. a kind ofly according to claim 1 prepare the method for the transparent antimicrobial coating of selfreparing based on laminated assembling technology, it is characterized in that: polyanion is one or more in hyaluronic acid, polyacrylic acid, sodium alginate, kayexalate, sulfonated polyether-ether-ketone, the sulfonation glucan.
4. a kind ofly according to claim 1 prepare the method for the transparent antimicrobial coating of selfreparing based on laminated assembling technology, it is characterized in that: the consumption mol ratio of polycation and polyanion is 1: 10～10: 1.
5. a kind ofly according to claim 1 prepare the method for the transparent antimicrobial coating of selfreparing based on laminated assembling technology, it is characterized in that: antiseptic is triclosan, metronidazole, Ceftriaxone Sodium, Cefazolin sodium, cephalosporin, silver nitrate, shitosan, gather in ε-lysine one or more.
6. a kind ofly according to claim 1 prepare the method for the transparent antimicrobial coating of selfreparing based on laminated assembling technology, it is characterized in that: surfactant is one or more in lauryl sodium sulfate, softex kw, benzyl cetyl chloride ammonium, the neopelex.
7. a kind of according to claim 1 method for preparing the transparent antimicrobial coating of selfreparing based on laminated assembling technology; It is characterized in that: solvent is water, acetone, ethanol, N, one or more in dinethylformamide, dimethyl sulfoxide (DMSO), chloroform, the carrene.
8. a kind ofly according to claim 1 prepare the method for the transparent antimicrobial coating of selfreparing based on laminated assembling technology, 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.
9. a kind ofly prepare the method for the transparent antimicrobial coating of selfreparing based on laminated assembling technology as claim 8 is said, 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.
10. a kind ofly according to claim 1 prepare the method for the transparent antimicrobial coating of selfreparing based on laminated assembling technology, it is characterized in that: substrate is quartz, optical glass, monocrystalline silicon, calcirm-fluoride, metal or plastics.
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