CN106221538B - A kind of preparation method and application of modified aqueous polyurethane antibacterial film - Google Patents
A kind of preparation method and application of modified aqueous polyurethane antibacterial film Download PDFInfo
- Publication number
- CN106221538B CN106221538B CN201610716103.7A CN201610716103A CN106221538B CN 106221538 B CN106221538 B CN 106221538B CN 201610716103 A CN201610716103 A CN 201610716103A CN 106221538 B CN106221538 B CN 106221538B
- Authority
- CN
- China
- Prior art keywords
- aqueous polyurethane
- essential oil
- preparation
- curried
- grass essential
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention belongs to antibiotic antiseptic and food fresh keeping packaging material or food processing machinery coatings arts, and in particular to a kind of curried grass essential oil/g-C3N4The preparation and application of composite modification aqueous polyurethane antimicrobial coating agent.By the way that curried grass essential oil is adsorbed onto g-C3N4In nano material, to reduce the volatilization of curried grass essential oil in use, to reduce the waste of curried grass essential oil, improve its utilization rate, achieve the purpose that long acting antibiotic and efficiently utilizes, then aqueous polyurethane antibiotic paint is modified with this composite material of preparation, improves the stability and antibacterial and mouldproof of coating itself.
Description
Technical field
The invention belongs to antibiotic antiseptic and food fresh keeping packaging material or food processing machinery coatings arts, specifically relate to
And a kind of curried grass essential oil/g-C3N4The preparation and application of composite modification aqueous polyurethane antimicrobial coating agent.
Background technique
The cured chrysanthemum of Italy also known as curry grass, originate in Mediterranean eastern region, belong to one kind of composite family, essential oil is wide
It is general to be applied in fragrance industry and aromatotherapy.Its main component has acetic acid flores aurantii vinegar, curcumene, nerol, firpene, tool
Strong wooden perfume (or spice), and the feeling of band point fragrance, have extraordinary anti-inflammatory, antiallergy, anti-oxidant, radiation protection, anti-spasm,
Antiviral, convergence, soft skin, promotes cytothesis, killing fungus, antifungal, calm and other effects at sterilization.Both at home and abroad about meaning
The patent of the big cured chrysanthemum of benefit has: Chinese patent CN102273492A discloses a kind of sanitizer formulations containing Italian strawflower；South Korea
Patent KR10117341B1 discloses a kind of composition that can be used for skin wrinkle resisting containing the cured chrysanthemum of Italy；French Patent (FRP)
FR2965729A1 discloses a kind of composition for being used to treat skin allergy containing Italian strawflower；French Patent (FRP)
FR2953402A1 disclose it is a kind of containing Italian strawflower for skin repair, and treatment hemotoncus, the combination of healing and inflammation
Object；It is special that Korean Patent KR20030046949A discloses a kind of composition South Korea that can promote skin regeneration containing Italian strawflower
Benefit discloses a kind of anti-inflammatory composition containing Italian strawflower；French Patent (FRP) FR2811899A1 discloses a kind of containing Italian wax
Antitumor, the antiviral composition of chrysanthemum；A kind of marine anticorrosion antifouling coating of containing graphene disclosed in CN104974640A
Preparation method sufficiently combines the good characteristic of two kinds of materials, and coating is made to have both the antifouling and big characteristic of anti-corrosion two.CN103589282A
A kind of marine anticorrosion antifouling coating and preparation method thereof of disclosed containing graphene, and coating is made to have both antifouling and anti-corrosion two greatly
Characteristic.Nanometer α-Fe disclosed in CN104277389A2O3Function modified PVA base compelx coating fresh-keeping packaging material and its preparation side
The packaging material of method, preparation has visible light catalytic bacteriostasis, preservation effect.
At present, curried grass essential oil is widely used in cosmetic industry and Chinese physical therapy field, Anhydroalkannin, anti-convulsion
Contraction, sterilization, cholagogue, diuresis, soft skin, resolving sputum, promotes cytothesis, killing fungus, sharp liver, calmness, benefit at antiviral, convergence
Spleen；Desalination scaring is feared, panic mood, it is stated that can also alleviate the mood of depression；Cured chrysanthemum essential oil is a kind of essential oil of return of spring,
It can promote cytothesis, help tissue reconstruction, and activate organ, degrading the channel.The threat of allergy and infectious disease can be lowered after use,
It is the good assistant of digestive organs, reduces the hyperemia phenomenon of liver and spleen, the not normal problem of processing gall-bladder adjusts point of pancreas and bile
It secretes, the recovery from illness of scar, acne, eczema, furuncle and abscess can be helped.But curried grass essential oil is volatile, exposure is unstable in air
It is fixed, so to find effective method reduces the degree of volatility of curried grass essential oil in use, extend its storage period.Cause
This, present invention nano material g-C3N4Essential oil is adsorbed.Nano material g-C3N4Specific surface area is larger, and due to it
It is that porous structure can effectively adsorb a large amount of essential oils.Secondly the g-C of essential oil will be adsorbed3N4It is mixed into the aqueous poly- ammonia of coating material
Modified antimicrobial coating is prepared in ester.
Aqueous polyurethane is with high-intensitive, high rigidity and with excellent fatigue performance and good flexibility etc..
The advantages of aqueous polyurethane is also equipped with different from solvent borne polyurethane simultaneously.Easily operate with performance, environmental protection it is nonirritant
It is smell, non-ignitable and be easily modified.These performances aqueous polyurethane to compare to be applied successfully to many fields, extensively
Substitution solvent borne polyurethane, such as mechanical surface coating, medical scaffold, ink bonding agent, and it is excellent to can be used as performance
Good coating dye for fabrics and the various functional coatings with specific function, such as self-clean type fungicidal paint, corrosion resistance
Coating and prominent optical coating etc..But the mildew resistance of aqueous polyurethane coating, weatherability, mechanical property and fungi-proofing property etc. influence
The principal element of coating performance, there is segmental defect, so we use the nano material of absorption essential oil in order to overcome these defects
It is modified.The characteristics such as skin effect specific to nano material, small size particles effect and track quantum effect, energy
Make up the heat resistance, water resistance and mechanical mechanics property of aqueous polyurethane significantly.Curried grass essential oil
Anti-corrosive antibacterial characteristic also can be improved the mould proof and fungi-proofing property of aqueous polyurethane coating.
Summary of the invention
The purpose of the present invention is open curried grass essential oil/g-C3N4The system of composite modification aqueous polyurethane antimicrobial coating
Preparation Method and application thereof, by the way that curried grass essential oil is adsorbed onto g-C3N4In nano material, used with reducing curried grass essential oil
Volatilization in journey improves its utilization rate to reduce the waste of curried grass essential oil, the mesh for reaching long acting antibiotic and efficiently utilizing
, then aqueous polyurethane antibiotic paint is modified with this composite material of preparation, improves the stability of coating itself
With antibacterial and mouldproof.
The present invention prepares nano material g-C by calcination method in vacuum tube furnace by urea3N4, heating rate be 5 DEG C/
Min, calcination temperature are 550 DEG C, calcination time 4h.
The present invention is by curried grass essential oil, nano material g-C3N4Curried grass essential oil/g-C is made with aqueous polyurethane coating3N4
The aqueous polyurethane antimicrobial coating agent of composite modification.
The preparation method is that first preparing nano material g-C by calcination method in vacuum tube furnace with urea3N4,
Curried grass essential oil is dissolved in nano material g-C again3N4In, then it is equal that aqueous polyurethane coating stirring is added in heated sealed stirring
Even and ultrasonic disperse obtains modified aqueous polyurethane antimicrobial coating agent except the gas in striping dispersion.
The heated sealed stirring refers to stirs for 24 hours in being sealed in 40 DEG C of baking ovens.
Metal iron plate is selected respectively, and sheet glass and plastic sheet are as sample bottom plate；In addition, being intended to for 3 kinds of sample bottom plates
It to be surface-treated in advance, be impregnated with the alcohol of 75% (V/V) and be ultrasonically treated 5-6h and clean naturally dry with distilled water again
Afterwards, modified aqueous polyurethane antimicrobial coating agent is uniformly applied to treated metal iron plate, sheet glass and modeling with scrubbing brush
On tablet, with a thickness of 1.0mm, it is put into insulating box 30 DEG C of freeze-day with constant temperature for 24 hours.
The metal iron plate, sheet glass and plastic sheet specification are food-grade, and size is 10mm × 10mm, metal iron plate
For the stainless steel substrates of 304 materials, sheet glass is high borosilicate material, and plastic sheet is PET material.
The nano material g-C3N4Mass ratio with curried grass essential oil is 1:1~5:1；The aqueous poly- ammonia of obtained modification
Nano material g-C in ester antimicrobial coating agent3N4The ratio between with the quality of curried grass essential oil and the volume of aqueous polyurethane are as follows: 0.04g/
mL。
The curried grass essential oil refers to the curried grass essential oil after dilution, and pure curried grass essential oil is added in dehydrated alcohol
The curried grass essential oil-that curried grass essential oil after obtaining the dilution that concentration expressed in percentage by volume is 10%, i.e. concentration expressed in percentage by volume are 10%
Ethanol solution.
By curried grass essential oil/nano material g-C of preparation3N4It is mixed into aqueous polyurethane coating, obtains the aqueous poly- of modification
Urethane antimicrobial coating agent, then coating agent is coated on the sample bottom plate prepared and probes into its various aspects of performance, curried grass essential oil/receive
Rice material g-C3N4Mass ratio is 1:5, and antibacterial effect is just more satisfactory when the concentration for being mixed into aqueous polyurethane is 0.04%,
The aqueous polyurethane antimicrobial coating agent surface roughness of the modification obtained under the conditions of this, hydrophobic performance, hardness, impact resistance and
Adhesion property is all more satisfactory.
Detailed description of the invention
The surface roughness of Fig. 1 modified polyurethane coating.
The coefficient of friction of Fig. 2 modified polyurethane coating.
The water contact angle of Fig. 3 modified polyurethane coating.
Fig. 4 modified polyurethane coating anti-metal on piece Staphylococcus Aureus Biofilm.
Staphylococcus Aureus Biofilm on the anti-sheet glass of Fig. 5 modified polyurethane coating.
Staphylococcus Aureus Biofilm on the anti-plastic sheet of Fig. 6 modified polyurethane coating.
1 curried grass essential oil of table/g-C3N4The percentage of water loss of composite modification aqueous polyurethane coating film.
Specific embodiment
Illustrate a specific embodiment of the invention, but protection content of the invention by following Examples, is not only limited to this.
1 curried grass essential oil of embodiment/g-C3N4The preparation of composite modification aqueous polyurethane coating film and its performance study
1 experimental material
Urea；AR；Sinopharm Chemical Reagent Co., Ltd..
Dehydrated alcohol；AR；Sinopharm Chemical Reagent Co., Ltd..
Curried grass essential oil；AR；French florihana essential oil.
Aqueous polyurethane；Qingdao of Shandong province Jie Ente Science and Technology Ltd..
2 experimental methods
1)g-C3N4Adsorb curried grass essential oil
1. weighing the curried grass essential oil of 160 μ L 100% (V/V), the dissolution of 1440 μ L dehydrated alcohols is added to be made into 10% (V/V)
Curried grass essential oil.
2. weighing 5 parts of 0.125g-C3N4Into 5mL centrifuge tube, add respectively according to mass ratio 1:1,1:2,1:3,1:4,1:5
After the curried grass essential oil for entering the 10% of different volumes, sealing stirring adsorbs it sufficiently at 40 DEG C.
3. by above-mentioned curried grass essential oil/g-C3N4Compound is added to aqueous polyurethane coating by the concentration of 0.04% (W/V)
In, it stirs evenly and ultrasonic disperse is except the gas in striping dispersion, be thus prepared for the modified curried of different ratio of adsorption
Careless essential oil/g-C3N4Aqueous polyurethane.
4. selecting the metal iron plate of 10mm × 10mm as sample bottom plate, this sample bottom plate will be carried out at surface in advance
Reason impregnates ultrasonic treatment 5-6h with the alcohol of 75% (V/V) and cleans naturally dry with distilled water again.
5. modified aqueous polyurethane to be uniformly applied to the gold of treated 6 10mm × 10mm respectively with scrubbing brush
Belong on iron plate, is put into insulating box 30 DEG C of freeze-day with constant temperature for 24 hours.
2) measurement of surface roughness
1. the metal iron plate for having brushed modified aqueous polyurethane (specification is 10mm × 10mm) is placed on surface roughness
On the workbench of measuring instrument (SRM-1 (D) type), the roughness Ra of coating surface is measured.
2. adjusting sensor, the position for being parallel to coating is reached.Check whether contact of the tested surface with sensor be good
It is good.
3. starting measuring instrument, sensor generates sliding, and does linear uniform motion, according to stopping after set distance back and forth movement
Only move.
4. measuring instrument depicts the micro-profile of coating surface, the floating motion curve relative to reference line is drawn out.
5. and the signal acquiring system by measuring instrument and arithmetic processing system obtain acquisition operation result, obtain coating
The roughness value on surface.
3) measurement of skin-friction coefficient
Coefficient of friction refer to two surfaces frictional force its effect vertical force on the contact surface ratio.Coefficient of friction and table
The raw sugar degree in face is related, and unrelated with contact area size, can be divided into dynamic friction and static friction.The mantle friction of coating
Coefficient is not only related with surface roughness, but also related with some performances and state of coating itself (impregnating, dry) etc..
This experiment uses bevel friction coefficient instrument, chooses the examination brushed specification is the drying of 10mm × 10mm metallic iron on piece
Sample.Sample is fixed on sample platform, the electronic induction of coating surface is placed on sample along block load；Friction coefficient instrument is opened,
Sample board at the uniform velocity rises, and starts the tilt angle for sliding moment, obtains the coefficient of friction of coating surface.
4) measurement of water contact angle
Contact angle on surface of coating is measured using contact measurement instrument in experiment.Before apparatus measures contact angle, it should will try
Sample removing surface is clean, and keeps drying.When testing contact angle, water droplet should be controlled in 3 μ L or so, be missed to reduce experiment number
Difference, this experiment survey 3 points using same sample at random, average.After water droplet to surface, every 3s automatic camera one is opened, altogether
Clap 11.Then the water contact angle of each frame is measured.
According to obtained contact angle dynamic picture, the timing from water droplet is contacted with coating surface takes the interval 10s for this experiment
Remember contact angle values, hereafter each minute takes a contact angle values, until stopping recording when 5min.
5) measurement of water resistance
Measurement applies the quality (M of cated metal iron plate0), it obtains impregnating slide specimen equipped with 250mL deionization
In the polytetrafluoroethylene box of water, certain time t is impregnated, the moisture on surface is taken out and blotted with filter paper with tweezers, measures its weight
Referred to as weight in wet base (M1) comparison initial weight, weight in wet base calculating water absorption rate, such as following formula
Wherein Ф is water absorption rate, %.
3 experimental results
1) surface roughness of coated film
Surface roughness is one of the important indicator for determining coating material and whether being applicable in.As shown in Figure 1, with doping quality
The surface roughness of the raising of ratio, coating is gradually reduced, and drops to 0.198 by 0.675.Experiment shows the g-C of addition3N4Afterwards,
Not only roughness is smaller, and the bumps of coating surface are more uniform, do not occur larger protrusion, show modified powder dispersion effect
Preferably.
2) coefficient of friction of coated film
It is similar to the surface roughness rule of coating, as shown in Figure 2, curried grass essential oil/g-C3N4Mass ratio is 1:0's
G-C is added 0.88 or more in the coefficient of friction of aqueous polyurethane coating3N4Later, the coefficient of friction of coating is reduced；With
g-C3N4The coefficient of friction of the increase of content, coating surface is substantially reduced.Curried grass essential oil/g-C3N4Mass ratio reach 1:3 it
Afterwards, decrease speed is slowed down.Experiment shows that curried grass essential oil/g-C is added3N4Later, the friction of polyurethane coating can be changed
Performance, drag-reduction effect are preferable.
3) water contact angle of coated film
Fig. 3 is the picture shot by contact angle measurement, measures water contact angle by software.From the figure 3, it may be seen that curried grass
Essential oil/g-C3N4Mass ratio is the water contact angle of the aqueous polyurethane coating of 1:0 as time change is obvious, and liquid is in coating table
Face is spread out rapidly, and contact angle becomes smaller, amplitude of variation 10.5%, and curried grass essential oil/g-C is added3N4Mass ratio is 1:5, with constantly
Between change less, contact angle size stablize, have stable hydrophobicity.Experiment shows that curried grass essential oil/g-C is added3N4It can be with
It is obviously improved the hydrophobic performance of aqueous polyurethane.
4) water resistance of coated film
Since coating composition is mainly aqueous polyurethane, so what is mainly reduced is aqueous poly- after coated and dried constant weight
The quality of urethane.As it can be seen from table 1 curried grass essential oil/g-C3N4Mass ratio is the weight-loss ratio of the aqueous polyurethane coating of 1:0
Reach 3.97%, and g-C is added3N4Coating weight-loss ratio afterwards gradually decreases to 2.37%.Coating foodstuffs weight-loss ratio has with water resistance
The reduction of much relations, weight-loss ratio keeps the water resistance of coating better, to obtain more stable coating structure.
1 curried grass essential oil of table/g-C3N4The weight-loss ratio of composite modification aqueous polyurethane coating film
Modified aqueous polyurethane coated film iron-resistant on piece Staphylococcus Aureus Biofilm effect prepared by embodiment 2 is ground
Study carefully
1 experimental material
1. modified aqueous polyurethane
2. staphylococcus aureus
2 experimental methods
1) preparation of bacterium solution
After directly taking the strain being inoculated in nutrient broth medium test tube, staphylococcus aureus to cultivate 48h, with vibration
After swinging device mixing, with 0 times of 0.03mol/L phosphate buffer 1,1000 times of gradient dilution (about 105cfu/mL)。
2) curried grass essential oil/g-C is prepared3N4Composite modification aqueous polyurethane coating film
It using 10mm × 10mm metal iron plate is sample bottom plate by the coffee of the different ratio of adsorption of preparation referring to above-described embodiment 1
Curry grass essential oil/g-C3N4Composite modification Aqueous Polyurethane Coating Agent brush is spare on iron plate surface.
3) preparation of control group sample liquid
The dilution bacterium solution that 0.5mL is drawn with liquid-transfering gun is added to the sterilized TSB solution containing 4.5mL and general
In the test tube of logical aqueous polyurethane coating metal iron plate.
4) preparation of test group sample liquid
The examination for having diluted bacterium solution liquid and being added to the sterilized TSB solution containing 4.5mL of 0.5mL is drawn with liquid-transfering gun
Guan Zhong fullys shake after shaking up, and the metal iron plate for the different ratio of adsorption for respectively preparing step 2 is added in above-mentioned test tube.
5) stationary culture
Test tube containing check sample and test sample is fixed in constant incubator, in 37 DEG C of ± 1 DEG C of items of operative temperature
Stationary culture 48h is under part to form biomembrane.
6) stationary culture count plate after a certain period of time
After stationary culture 48h, iron plate is pressed from both sides out, is gently rinsed 3 times with the PBS buffer solution of sterilizing, is finally sandwiched and go out
In the centrifuge tube of the 10mL of bacterium, the PBS buffer solution ultrasound 10min that 3mL is added is crushed biomembrane, and bacterium is formed in centrifuge tube
Suspension.By the control sample liquid in centrifuge tube containing staphylococcus aureus and sample liquid is tested after 10 times 100 times of gradient dilution,
0.1mL stoste, 10 are drawn respectively-1、10-2With 10-3Times sample liquid is coated on nutritious agar medium plate, every sample liquid
2 plates of coating in parallel are inverted in culture 48h in 37 DEG C of ± 1 DEG C of constant incubators and do viable bacteria culture counting.
7) data processing
According to the viable bacteria clump count recorded, the Staphylococcus aureus in each sample liquid after contact concussion for 24 hours is calculated
The total viable count of bacterium, control, it was therefore concluded that.
3 experimental results
As shown in Figure 4, with curried grass essential oil/g-C3N4The anti-microbial property of the increase of mass ratio, aqueous polyurethane coating has
Increased.Curried grass essential oil/g-C3N4When mass ratio is 1:0, remaining bacterium number is 5.9lg (cfu/cm2)；Curried grass essential oil/g-
C3N4When mass ratio is 1:5, remaining bacterium number is 5.1lg (cfu/cm2)；It is above-mentioned the experimental results showed that by curried grass essential oil/g-
C3N4Modified polyurethane coating, coating to the sheet metal containing Staphylococcus Aureus Biofilm after 48h, have preferable antibacterial
Performance.
Staphylococcus Aureus Biofilm effect on the anti-sheet glass of modified aqueous polyurethane coated film prepared by embodiment 3
Research
1 experimental material
1. modified aqueous polyurethane
2. staphylococcus aureus
2 experimental methods
1) preparation of bacterium solution
After directly taking the strain being inoculated in nutrient broth medium test tube, staphylococcus aureus to cultivate 48h, with vibration
After swinging device mixing, with 0 times of 0.03mol/L phosphate buffer 1,1000 times of gradient dilution (about 105cfu/mL)。
2) curried grass essential oil/g-C is prepared3N4Composite modification aqueous polyurethane coating film
It using 10mm × 10mm sheet glass is sample bottom plate by the curry of the different ratio of adsorption of preparation referring to above-described embodiment 1
Careless essential oil/g-C3N4Composite modification Aqueous Polyurethane Coating Agent brush is spare in glass sheet surface.
3) preparation of control group sample liquid
The dilution bacterium solution that 0.5mL is drawn with liquid-transfering gun is added to the sterilized TSB solution containing 4.5mL and general
In the test tube of logical aqueous polyurethane coating sheet glass.
4) preparation of test group sample liquid
The examination for having diluted bacterium solution liquid and being added to the sterilized TSB solution containing 4.5mL of 0.5mL is drawn with liquid-transfering gun
Guan Zhong fullys shake after shaking up, and the sheet glass for the different ratio of adsorption for respectively preparing step 2 is added in above-mentioned test tube.
5) stationary culture
Test tube containing check sample and test sample is fixed in constant incubator, in 37 DEG C of ± 1 DEG C of items of operative temperature
Stationary culture 48h is under part to form biomembrane.
6) stationary culture count plate after a certain period of time
After stationary culture 48h, sheet glass is pressed from both sides out, is gently rinsed 3 times with the PBS buffer solution of sterilizing, is finally sandwiched
In the centrifuge tube of the 10mL of sterilizing, the PBS buffer solution ultrasound 10min that 3mL is added is crushed biomembrane, is formed in centrifuge tube thin
Bacterium suspension.By the control sample liquid in centrifuge tube containing staphylococcus aureus and sample liquid is tested through 10 times 100 times of gradient dilution
Afterwards, 0.1mL stoste, 10 are drawn respectively-1、10-2With 10-3Times sample liquid is coated on nutritious agar medium plate, every sample
Liquid is coated with 2 plates in parallel, is inverted in culture 48h in 37 DEG C of ± 1 DEG C of constant incubators and does viable bacteria culture counting.
7) data processing
According to the viable bacteria clump count recorded, the Staphylococcus aureus in each sample liquid after contact concussion for 24 hours is calculated
The total viable count of bacterium, control, it was therefore concluded that.
3 experimental results
As shown in Figure 5, with curried grass essential oil/g-C3N4The anti-microbial property of the increase of mass ratio, aqueous polyurethane coating has
Increased.Curried grass essential oil/g-C3N4When mass ratio is 1:0, remaining bacterium number is 5.8lg (cfu/cm2)；Curried grass essential oil/g-
C3N4When mass ratio is 1:5, remaining bacterium number is 5.1lg (cfu/cm2)；It is above-mentioned the experimental results showed that by curried grass essential oil/g-
C3N4Modified polyurethane coating, coating to the sheet glass containing Staphylococcus Aureus Biofilm after 48h, have preferable antibacterial
Performance.
Staphylococcus Aureus Biofilm effect grinds on the anti-plastics of modified aqueous polyurethane coated film prepared by embodiment 4
Study carefully
1 experimental material
1. modified aqueous polyurethane
2. staphylococcus aureus
2 experimental methods
1) preparation of bacterium solution
After directly taking the strain being inoculated in nutrient broth medium test tube, staphylococcus aureus to cultivate 48h, with vibration
After swinging device mixing, with 0 times of 0.03mol/L phosphate buffer 1,1000 times of gradient dilution (about 105cfu/mL)。
2) curried grass essential oil/g-C is prepared3N4Composite modification aqueous polyurethane coating film
It using 10mm × 10mm plastic sheet is sample bottom plate by the curry of the different ratio of adsorption of preparation referring to above-described embodiment 1
Careless essential oil/g-C3N4Composite modification Aqueous Polyurethane Coating Agent brush is spare in plastic sheet surface.
3) preparation of control group sample liquid
The dilution bacterium solution that 0.5mL is drawn with liquid-transfering gun is added to the sterilized TSB solution containing 4.5mL and general
In the test tube of logical aqueous polyurethane coating plastic sheet.
4) preparation of test group sample liquid
The examination for having diluted bacterium solution liquid and being added to the sterilized TSB solution containing 4.5mL of 0.5mL is drawn with liquid-transfering gun
Guan Zhong fullys shake after shaking up, and the plastic sheet for the different ratio of adsorption for respectively preparing step 2 is added in above-mentioned test tube.
5) stationary culture
Test tube containing check sample and test sample is fixed in constant incubator, in 37 DEG C of ± 1 DEG C of items of operative temperature
Stationary culture 48h is under part to form biomembrane.
6) stationary culture count plate after a certain period of time
After stationary culture 48h, plastic sheet is pressed from both sides out, is gently rinsed 3 times with the PBS buffer solution of sterilizing, is finally sandwiched
In the centrifuge tube of the 10mL of sterilizing, the PBS buffer solution ultrasound 10min that 3mL is added is crushed biomembrane, is formed in centrifuge tube thin
Bacterium suspension.By the control sample liquid in centrifuge tube containing staphylococcus aureus and sample liquid is tested through 10 times 100 times of gradient dilution
Afterwards, 0.1mL stoste, 10 are drawn respectively-1、10-2With 10-3Times sample liquid is coated on nutritious agar medium plate, every sample
Liquid is coated with 2 plates in parallel, is inverted in culture 48h in 37 DEG C of ± 1 DEG C of constant incubators and does viable bacteria culture counting.
7) data processing
According to the viable bacteria clump count recorded, the Staphylococcus aureus in each sample liquid after contact concussion for 24 hours is calculated
The total viable count of bacterium, control, it was therefore concluded that.
3 experimental results
As shown in Figure 5, with curried grass essential oil/g-C3N4The anti-microbial property of the increase of mass ratio, aqueous polyurethane coating has
Increased.Curried grass essential oil/g-C3N4When mass ratio is 1:0, remaining bacterium number is 6.2lg (cfu/cm2)；Curried grass essential oil/g-
C3N4When mass ratio is 1:5, remaining bacterium number is 5.7lg (cfu/cm2)；It is above-mentioned the experimental results showed that by curried grass essential oil/g-
C3N4Modified polyurethane coating, coating to the plastic sheet containing Staphylococcus Aureus Biofilm after 48h, have preferable antibacterial
Performance.
Claims (8)
1. a kind of preparation method of modified aqueous polyurethane antibacterial film, it is characterised in that: curried grass essential oil is dissolved in a nanometer material
Expect g-C3N4In, heated sealed stirring, then addition aqueous polyurethane coating stirs evenly and ultrasonic disperse is except striping dispersion
In gas, obtain modified aqueous polyurethane antimicrobial coating agent；Using nano material g-C3N4Curried essential oil is adsorbed,
The nano material g-C of curried essential oil will be adsorbed3N4It is mixed into aqueous polyurethane coating, improves the surface of aqueous polyurethane coating
Roughness, frictional behaviour, hydrophobic performance, water resistance, and assign aqueous polyurethane coating anti-microbial property.
2. a kind of preparation method of modified aqueous polyurethane antibacterial film as described in claim 1, it is characterised in that: nano material
g-C3N4It is prepared in vacuum tube furnace by calcination method by urea, heating rate is 5 DEG C/min, and calcination temperature is 550 DEG C, is forged
The burning time is 4h.
3. a kind of preparation method of modified aqueous polyurethane antibacterial film as described in claim 1, it is characterised in that: the sealing
Heating stirring, which refers to be sealed in 40 DEG C of baking ovens, to be stirred for 24 hours.
4. a kind of preparation method of modified aqueous polyurethane antibacterial film as described in claim 1, it is characterised in that: the curry
Careless essential oil and nano material g-C3N4Mass ratio be 1:1~1:5；It is received in the aqueous polyurethane antimicrobial coating agent of obtained modification
Rice material g-C3N4The ratio between with the quality sum of curried grass essential oil and the volume of aqueous polyurethane are as follows: 0.04g/mL.
5. a kind of preparation method of modified aqueous polyurethane antibacterial film as described in claim 1, it is characterised in that: the coffee
Curry grass essential oil refers to the curried grass essential oil after dilution, and pure curried grass essential oil is added in dehydrated alcohol and obtains concentration expressed in percentage by volume
For the curried grass essential oil after 10% dilution, i.e., concentration expressed in percentage by volume be 10% curried grass essential oil-ethanol solution.
6. a kind of preparation method of modified aqueous polyurethane antibacterial film as claimed in claim 4, it is characterised in that: the curry
Careless essential oil and nano material g-C3N4Mass ratio be 1:5.
7. a kind of preparation method of modified aqueous polyurethane antibacterial film as described in claim 1, it is characterised in that: select respectively
Metal iron plate, sheet glass and plastic sheet are as sample bottom plate；It for 3 kinds of sample bottom plates, is intended to be surface-treated in advance, use
The alcohol of 75% (V/V) impregnates and is ultrasonically treated 5-6h to be cleaned after natural drying with distilled water again, will be modified aqueous with scrubbing brush
Polyurethane antibiotic coating agent is uniformly applied to treated metal iron plate, on sheet glass and plastic sheet, with a thickness of 1.0mm, puts
Enter in insulating box 30 DEG C of freeze-day with constant temperature for 24 hours.
8. a kind of preparation method of modified aqueous polyurethane antibacterial film as claimed in claim 7, it is characterised in that: the metal
Iron plate, sheet glass and plastic sheet specification are food-grade, and size is 10mm × 10mm, and metal iron plate is the stainless of 304 materials
Steel disc, sheet glass are high borosilicate material, and plastic sheet is PET material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610716103.7A CN106221538B (en) | 2016-08-24 | 2016-08-24 | A kind of preparation method and application of modified aqueous polyurethane antibacterial film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610716103.7A CN106221538B (en) | 2016-08-24 | 2016-08-24 | A kind of preparation method and application of modified aqueous polyurethane antibacterial film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106221538A CN106221538A (en) | 2016-12-14 |
| CN106221538B true CN106221538B (en) | 2019-06-28 |
Family
ID=57554497
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610716103.7A Active CN106221538B (en) | 2016-08-24 | 2016-08-24 | A kind of preparation method and application of modified aqueous polyurethane antibacterial film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106221538B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106634129A (en) * | 2016-12-29 | 2017-05-10 | 常德市金润新材料科技有限公司无锡新材料研究院 | Mildewproof preservative film and preparation method thereof |
| CN107880525A (en) * | 2017-11-13 | 2018-04-06 | 常州凯恒纺织品有限公司 | A kind of keyboard protective film |
| CN109054621A (en) * | 2018-06-27 | 2018-12-21 | 滁州环球聚氨酯科技有限公司 | A kind of preparation method for the packaging film polyurethane coating extending effective period of food quality |
| CN109749136A (en) * | 2019-02-25 | 2019-05-14 | 牟富书 | A kind of degradable anti-bacterial refreshing membrane product and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105664991A (en) * | 2016-02-22 | 2016-06-15 | 南开大学 | Method for preparing efficient bactericide silver/graphite phase carbon nitride composite material |
| CN105728010A (en) * | 2016-02-02 | 2016-07-06 | 常州大学 | Preparation method of antibacterial silver molybdate and graphite-phase carbon nitride composite visible-light-induced photocatalyst |
-
2016
- 2016-08-24 CN CN201610716103.7A patent/CN106221538B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105728010A (en) * | 2016-02-02 | 2016-07-06 | 常州大学 | Preparation method of antibacterial silver molybdate and graphite-phase carbon nitride composite visible-light-induced photocatalyst |
| CN105664991A (en) * | 2016-02-22 | 2016-06-15 | 南开大学 | Method for preparing efficient bactericide silver/graphite phase carbon nitride composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106221538A (en) | 2016-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106221538B (en) | A kind of preparation method and application of modified aqueous polyurethane antibacterial film | |
| Manabe et al. | Porous surface structure fabricated by breath figures that suppresses Pseudomonas aeruginosa biofilm formation | |
| Choi et al. | Superhydrophilic coatings with intricate nanostructure based on biotic materials for antifogging and antibiofouling applications | |
| Xiao et al. | Novel robust superhydrophobic coating with self-cleaning properties in air and oil based on rare earth metal oxide | |
| Di Ciccio et al. | Biofilm formation by Staphylococcus aureus on food contact surfaces: Relationship with temperature and cell surface hydrophobicity | |
| Turalija et al. | Antimicrobial PLA films from environment friendly additives | |
| Aldosari et al. | Using ZnO nanoparticles in fungal inhibition and self-protection of exposed marble columns in historic sites | |
| CN106221540B (en) | The Preparation method and use of modified aqueous polyurethane antimicrobial coating | |
| Su et al. | Stearic acid-modified starch/chitosan composite sponge with asymmetric and gradient wettability for wound dressing | |
| Galante et al. | Superhemophobic and antivirofouling coating for mechanically durable and wash-stable medical textiles | |
| Araújo et al. | Control of microbial adhesion as a strategy for food and bioprocess technology | |
| Esmeryan et al. | Early stage anti-bioadhesion behavior of superhydrophobic soot based coatings towards Pseudomonas putida | |
| Mitik-Dineva et al. | Differences in colonisation of five marine bacteria on two types of glass surfaces | |
| Ploux et al. | Quantitative and morphological analysis of biofilm formation on self-assembled monolayers | |
| CN106538583B (en) | Long-acting disinfection bactericidal composition, its coating method and the regeneration method for coating | |
| Wang et al. | Liquid‐Like SiO2‐g‐PDMS Coatings on Wood Surfaces with Underwater Durability, Antifouling, Antismudge, and Self‐Healing Properties | |
| Kuyukina et al. | Diverse effects of a biosurfactant from Rhodococcus ruber IEGM 231 on the adhesion of resting and growing bacteria to polystyrene | |
| Mu et al. | Influence of surface roughness, nanostructure, and wetting on bacterial adhesion | |
| Dufrěne et al. | Direct evidence for the involvement of extracellular proteins in the adhesion of Azospirillum brasilense | |
| Sontakke et al. | Nano ZnO grafted on MAA/BA/MMA copolymer: an additive for hygienic coating | |
| Winandy et al. | Fungal hydrophobins render stones impermeable for water but keep them permeable for vapor | |
| Choi et al. | Achieving antifingerprinting and antibacterial effects in smart-phone panel applications using ZnO thin films without a protective layer | |
| Cao et al. | Superhydrophobic fluorinated oligomers as protective agents for outdoor stone artworks | |
| CN106349902B (en) | The Preparation method and use of nanocomposite modified aqueous polyurethane antimicrobial coating | |
| Fujimoto et al. | Cicada-wing-inspired nanopillar hydrogels consisting of poly (vinyl alcohol) and poly (methacrylic acid) for capturing bacteria through their flexibility and wide range of motion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |