CN107151507A - A kind of preparation method of environment-friendly type antimildew and antibacterial coated film - Google Patents
A kind of preparation method of environment-friendly type antimildew and antibacterial coated film Download PDFInfo
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- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
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- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
- C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
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- 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
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
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- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/385—Oxides, hydroxides or carbonates
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- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
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- D21H19/00—Coated paper; Coating material
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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Abstract
A kind of preparation method of environment-friendly type antimildew and antibacterial coated film disclosed by the invention, is comprised the steps of：Sulfamic acid is added after adding modified epoxy, curing agent, stirring 1h in a kettle., modified silicasol is added, is eventually adding deionized water, the emulsion that solid content is 30 60% is obtained；The emulsion that mass fraction is 100 parts, the mill base material that mass fraction is 50 parts, the deionized water that mass fraction is 200 500 parts are mixed；Application is carried out to it using water paint on substrate, 20 30min are toasted after application in 120 170 DEG C of baking oven, film thickness monitoring is at 18 22 microns.The preparation method of the environment-friendly type antimildew and antibacterial coated film, the effective antimildew and antibacterial of coated film energy of preparation, and the coated film is based on water paint, environmental protection, and there is excellent corrosion resistance, good weatherability properties, scratch-resistant.
Description
Technical field
The present invention relates to the technical field of coating film preparation, more particularly to a kind of preparation of environment-friendly type antimildew and antibacterial coated film
Method.
Background technology
Continuous improvement and the constantly improve of environmental regulation with environmental consciousness, external coating industry is to volatile organic
The control of compound content and harmful substance contents is further strict, and the Water-borne modification of coating and the trend of powdered are more and more obvious.
And what the film forming matter of coating was made up of a variety of natural or synthetic high-molecular compounds, most of these materials contain biology
Nutrients required for growth, is protected biological resistance if water paint lacks, and after film forming mould and algae can be caused a large amount of
Grow and influence its performance.Therefore, based on water paint film forming, it is necessary to develop a kind of environment-friendly type antimildew and antibacterial coating and
Coated film based on the coating.
The content of the invention
It is an object of the invention to provide a kind of preparation method of environment-friendly type antimildew and antibacterial coated film, above-mentioned prior art is solved
One or more in problem.
A kind of environment-friendly type antimildew and antibacterial coating membrane preparation method that the present invention is provided, is comprised the steps of：
Sulfamic acid, 60-68 DEG C point of temperature are added after A1, in a kettle. addition modified epoxy, curing agent, stirring 1h
1-2h is dissipated, modified silicasol is added, vacuum distillation after deionized water, emulsification 30-50min is eventually adding and removes having in emulsion
Machine solvent, obtains the emulsion that solid content is 30-60%；
A2, it is that the obtained emulsion of 100 parts of A1, the mill base material that mass fraction is 50 parts, mass fraction are 200- by mass fraction
500 parts of deionized water mixing, obtains environment-friendlywater-based water-based paint；
A3, the water paint obtained on substrate using A2 carry out application to it, are toasted after application in 120-170 DEG C of baking oven
20-30min, film thickness monitoring is at 18-22 microns.
In some embodiments, the preparation method of modified epoxy is：By the epoxy novolac that mass fraction is 100 parts
The chain extender mixing that resin, mass fraction are 20-50 parts of epoxy resin and mass fraction is 1-10 parts, adds catalyst, anti-
Answer temperature to be reacted at 150 DEG C -180 DEG C, when epoxide equivalent reaches 1000-2200g/mol, cool the temperature to 60-80 DEG C,
Organic amine compound is subsequently added, amination and chain extending reaction are carried out between 90 DEG C -110 DEG C, the modified epoxy is obtained.
In some embodiments, novolac epoxy resin includes phenol type novolac epoxy resin, orthoresol type epoxy novolac
Any one or more of resin, bisphenol A-type novolac epoxy resin；
Wherein, epoxy resin includes bisphenol A type epoxy resin, bisphenol-s epoxy resin, bisphenol f type epoxy resin, polyethylene glycol
Any one or more of diglycidyl ether and polypropylene glycol diglycidyl ether；
Wherein, chain extender includes single phenol, bisphenol compound, bisphenol A-type PPG, dicarboxylic acids, PPG, two
Any one or more in first mercapto alcohol；
Wherein, catalyst includes triethanolamine, triethylamine, diethylamine, triphenyl phosphorus, tri-phenyl-phosphorus bromide, dimethyl benzylamine, miaow
Any one or more in azoles, methylimidazole, 2- ethyl 4-methylimidazoles；
Wherein, organic amine compound includes butylamine, diethylamine, methyl butyl amine, MEA, diethanol amine, N- methyl ethanols
Any one or more in amine, 1,3- dimethyl propylamines, N, N- dimethyl ethanols amino acid salt or kitimine organic amine.
In some embodiments, curing agent includes vinyl triamine, aminoethyl piperazine, m-phenylene diamine (MPD), diaminourea hexichol
Base add in any one or more.
In some embodiments, the preparation method of modified silicasol comprises the following steps：
B1, with uniform particle sizes, size 20-40nm, proportion is used as crystal seed, 10-15 for 1.10-1.15 alkaline silicon dioxide colloidal sol
Times deionized water is diluted, and it is 10-12 to adjust pH value by mass fraction 4-6% potassium hydroxide solutions；Gained mixed liquor is carried out
Heating, temperature control is continuously added into proportion for 1.00-1.04 in 100-105 DEG C, heating process, and pH value is 2.0-3.0 silicon
Acid, to maintain liquid level constant；
B2, by molar fraction be 0.1-1% meta-aluminic acids, pass through dispersed with stirring to mass fraction be 5-10% NaOH and triethanolamine
Mixed solution in, and during the course of the reaction, the mixed solution containing aluminium described in 50-100ml was added every 1-3 hours, to maintain
The pH of reaction solution is between 9.0-10.0；
B3, by the reaction solution continuous heating time it is 50-60h, when the silicon dioxide gel proportion is reached 1.250-1.300, stops
Heating, reaction terminates, and finally obtains pH for 9.0-9.8, and particle diameter is 100-120nm modified silicasol.
In some embodiments, the preparation method of mill base material is：The epoxy that mass fraction is 100 parts is added in reactor
Resin, mass fraction are 10-20 parts of titanium oxide, the kaolin of 20-25 parts of mass fraction, the carbon black that mass fraction is 1-5 parts
Deionized water with mass fraction is 200-300 parts, is sanded after 10-15h, obtaining solid content is after being well mixed with ball mill
40-60% mill base material.
In some embodiments, substrate be metal, glass, natural resin, synthetic resin, ceramics, timber, paper, fiber,
Non-woven fabrics, weave cotton cloth or leather in one or more.
A kind of preparation method of environment-friendly type antimildew and antibacterial coated film, is comprised the steps of：
C1, be 100 parts of novolac epoxy resin by mass fraction, mass fraction is 20-50 parts of epoxy resin and mass fraction is
1-10 parts of chain extender mixing, adds catalyst, is reacted in reaction temperature at 150 DEG C -180 DEG C, when epoxide equivalent reaches
1000-2200g/mol, cools the temperature to 60-80 DEG C, is subsequently added organic amine compound, is carried out between 90 DEG C -110 DEG C
Amination and chain extending reaction, obtain the modified epoxy；
C2, with uniform particle sizes, size 20-40nm, proportion is used as crystal seed, 10-15 for 1.10-1.15 alkaline silicon dioxide colloidal sol
Times deionized water is diluted, and it is 10-12 to adjust pH value by mass fraction 4-6% potassium hydroxide solutions；Gained mixed liquor is carried out
Heating, temperature control is continuously added into proportion for 1.00-1.04 in 100-105 DEG C, heating process, and pH value is 2.0-3.0 silicon
Acid, to maintain liquid level constant；
C3, by molar fraction be 0.1-1% meta-aluminic acids, pass through dispersed with stirring to mass fraction be 5-10% NaOH and triethanolamine
Mixed solution in, and during the course of the reaction, the mixed solution containing aluminium described in 50-100ml was added every 1-3 hours, to maintain
The pH of reaction solution is between 9.0-10.0；
C4, by the reaction solution continuous heating time it is 50-60h, when the silicon dioxide gel proportion is reached 1.250-1.300, stops
Heating, reaction terminates, and finally obtains pH for 9.0-9.8, and particle diameter is 100-120nm modified silicasol；
Sulfamic acid, 60-68 DEG C point of temperature are added after C5, in a kettle. addition modified epoxy, curing agent, stirring 1h
1-2h is dissipated, modified silicasol is added, vacuum distillation after deionized water, emulsification 30-50min is eventually adding and removes having in emulsion
Machine solvent, obtains the emulsion that solid content is 30-60%；
C6, in a kettle. the addition titanium oxide that mass fraction is 100 parts of epoxy resin, mass fraction is 10-20 parts, quality
The kaolin that 20-25 part of number, the carbon black that mass fraction is 1-5 parts and the deionized water that mass fraction is 200-300 parts, mixing
It is sanded after uniform with ball mill after 10-15h, obtains the mill base material that solid content is 40-60%；
C7, it is that the obtained emulsion of 100 parts of C5, the mill base material that mass fraction is 50 parts, mass fraction are 200- by mass fraction
500 parts of deionized water mixing, obtains environment-friendlywater-based water-based paint；
C8, the water paint obtained on substrate using C7 carry out application to it, are toasted after application in 120-170 DEG C of baking oven
20-30min, film thickness monitoring is at 18-22 microns.
Antimildew and antibacterial mechanism：The aluminium element for mixing aluminium in the present invention has stronger oxidability, can destroy bacterial cell
Metabolism, so as to hinder bacterial growth to breed, and after metal ion contact bacterium, because electrostatic attraction effect makes both tight
Close combination, causes metal ion energy penetration cell film to enter bacterium intracellular, then reacted with the thin base of intracellular protein so that egg
White matter solidify, cause bacterium can not schizogamy so that it is dead.On the other hand, electricity can be produced after silica is irradiated by light
Son-hole pair, it is a catalytic active center, can absorb the oxygen in the energy in environment, active material superficial air or water
Gas, generation hydroxyl radical free radical and superoxide anion radical, the two all has very strong redox ability, can aoxidize also
The organic matter of indigenous bacteria, so as to destroy the fertility of bacterium, reaches antibacterial effect.The free radical for reacting production is very active,
It can be reacted with the toxin of bacterium and its secretion, understand bacterium remains and toxin, moreover it is possible to generation hydroxyl is further acted on water and double
Oxygen water, hydrogen peroxide can pass freely through bacterial cell membrane, can not only kill bacterium, moreover it is possible to the endotoxin that decomposing bacteria after death discharges.
Embodiment
The present invention is described in more detail below by embodiment.
Case study on implementation 1：
A1, by mass fraction be 100 parts phenol type novolac epoxy resin, mass fraction be 20 parts of bisphenol A type epoxy resins and
Mass fraction mixes for 1 part of bisphenol A-type PPG, adds catalyst triethanolamine, in reaction temperature in 150 DEG C of progress
Reaction, when epoxide equivalent reaches 1000g/mol, cools the temperature to 60 DEG C, is subsequently added diethylamine, is carried out between 90 DEG C DEG C
Amination and chain extending reaction, obtain the modified epoxy；
A2, with uniform particle sizes, size 20nm, proportion is used as crystal seed, 10 times of deionized waters for 1.10 alkaline silicon dioxide colloidal sol
It is diluted, it is 10 to adjust pH value by the potassium hydroxide solution of mass fraction 4%；Gained mixed liquor is heated, and temperature control exists
100 DEG C, it is 1.00 that proportion is continuously added into heating process, and pH value is 2.0 silicic acid, to maintain liquid level constant；
A3, by molar fraction be 0.1% meta-aluminic acid, by dispersed with stirring to mass fraction for 5% NaOH and triethanolamine it is mixed
Close in solution, and during the course of the reaction, the mixed solution containing aluminium described in 50ml was added every 1 hour, with the pH of maintenance reaction liquid
9.0；
A4, by the reaction solution continuous heating time it is 50h, when the silicon dioxide gel proportion is reached 1.250, stops heating, reaction
Terminate, it is 9.0 to finally obtain pH, particle diameter is 100nm modified silicasol；
Sulfamic acid, temperature 60 C are added after a5, in a kettle. addition modified epoxy, vinyl triamine, stirring 1h
Scattered 1h, adds modified silicasol, is eventually adding organic in vacuum distillation removing emulsion after deionized water, emulsification 30min
Solvent, obtains the emulsion that solid content is 30%；
A6, in a kettle. the addition titanium oxide that mass fraction is 100 parts of epoxy resin, mass fraction is 10 parts, mass parts
The kaolin that 20 part of number, the carbon black that mass fraction is 1 part and the deionized water that mass fraction is 200 parts, it is well mixed after use ball
Grinding machine is sanded after 10h, obtains the mill base material that solid content is 40%；
A7, it is that the obtained emulsion of 100 parts of a5, the mill base material that mass fraction is 50 parts, mass fraction are 200 parts by mass fraction
Deionized water mixing, obtain environment-friendlywater-based water-based paint；
A8, the water paint obtained on base plate glass using a7 carry out application to it, after application in 120-170 DEG C of baking oven
20min is toasted, the coated film a that thickness is 18 microns is obtained.
Case study on implementation 2：
B1, by mass fraction be 100 parts bisphenol A-type novolac epoxy resin, mass fraction be 30 parts of bisphenol f type epoxy resins and
Mass fraction mixes for 5 parts of bisphenol A-type PPG, adds catalyst methylimidazole, enters in reaction temperature at 160 DEG C
Row reaction, when epoxide equivalent reaches 1800g/mol, cools the temperature to 70 DEG C, is subsequently added N, N- dimethyl ethanol amino acid salts,
Amination and chain extending reaction are carried out at 100 DEG C, the modified epoxy is obtained；
B2, with uniform particle sizes, size 30nm, proportion is used as crystal seed, 12 times of deionized waters for 1.12 alkaline silicon dioxide colloidal sol
It is diluted, it is 11 to adjust pH value by the potassium hydroxide solution of mass fraction 5%；Gained mixed liquor is heated, and temperature control exists
102 DEG C, it is 1.02 that proportion is continuously added into heating process, and pH value is 2.5 silicic acid, to maintain liquid level constant；
B3, by molar fraction be 0.5% meta-aluminic acid, by dispersed with stirring to mass fraction for 8% NaOH and triethanolamine it is mixed
Close in solution, and during the course of the reaction, the mixed solution containing aluminium described in 50-100ml was added every 2 hours, with maintenance reaction liquid
PH 9.5；
B4, by the reaction solution continuous heating time it is 55h, when the silicon dioxide gel proportion is reached 1.258, stops heating, reaction
Terminate, it is 9.5 to finally obtain pH, particle diameter is 110nm modified silicasol；
Sulfamic acid, 65 DEG C points of temperature are added after b5, in a kettle. addition modified epoxy, m-phenylene diamine (MPD), stirring 1h
1.5h is dissipated, modified silicasol is added, is eventually adding organic in vacuum distillation removing emulsion after deionized water, emulsification 40min
Solvent, obtains the emulsion that solid content is 50%；
B6, in a kettle. the addition titanium oxide that mass fraction is 100 parts of epoxy resin, mass fraction is 15 parts, mass parts
The kaolin that 22 part of number, the carbon black that mass fraction is 2 parts and the deionized water that mass fraction is 250 parts, it is well mixed after use ball
Grinding machine is sanded after 12h, obtains the mill base material that solid content is 50%；
B7, it is that the obtained emulsion of 100 parts of b5, the mill base material that mass fraction is 50 parts, mass fraction are 300 parts by mass fraction
Deionized water mixing, obtain environment-friendlywater-based water-based paint；
B8, the water paint obtained on substrate using b7 is subjected to application to it, toasted after application in 150 DEG C of baking oven
25min, obtains the coated film b that thickness is 20 microns.
Case study on implementation 3：
C1, by mass fraction be 100 parts orthoresol type novolac epoxy resin, mass fraction be 50 parts of bisphenol-s epoxy resins
Mixed with mass fraction for 10 parts of single phenol, add diethylamine, reacted in reaction temperature at 180 DEG C, when epoxide equivalent reaches
To 2200g/mol, 80 DEG C are cooled the temperature to, MEA is subsequently added, amination and chain extending reaction are carried out between 110 DEG C, is obtained
To the modified epoxy；
C2, with uniform particle sizes, size 40nm, proportion is used as crystal seed, 15 times of deionized waters for 1.15 alkaline silicon dioxide colloidal sol
It is diluted, it is 12 to adjust pH value by the potassium hydroxide solution of mass fraction 6%；Gained mixed liquor is heated, and temperature control exists
105 DEG C, it is 1.04 that proportion is continuously added into heating process, and pH value is 3.0 silicic acid, to maintain liquid level constant；
C3, by molar fraction be 1% meta-aluminic acid, pass through dispersed with stirring to mass fraction for 10% NaOH and triethanolamine mixing
In solution, and during the course of the reaction, every the mixed solution containing aluminium described in 3 hours addition 100ml, existed with the pH of maintenance reaction liquid
10.0；
C4, by the reaction solution continuous heating time it is 60h, when the silicon dioxide gel proportion is reached 1.300, stops heating, reaction
Terminate, it is 9.8 to finally obtain pH, particle diameter is 120nm modified silicasol；
Sulfamic acid, 68 DEG C of temperature are added after c5, in a kettle. addition modified epoxy, aminoethyl piperazine, stirring 1h
Scattered 2h, adds modified silicasol, is eventually adding organic in vacuum distillation removing emulsion after deionized water, emulsification 50min
Solvent, obtains the emulsion that solid content is 60%；
C6, in a kettle. the addition titanium oxide that mass fraction is 100 parts of epoxy resin, mass fraction is 20 parts, mass parts
The kaolin that 25 part of number, the carbon black that mass fraction is 5 parts and the deionized water that mass fraction is 300 parts, it is well mixed after use ball
Grinding machine is sanded after 15h, obtains the mill base material that solid content is 60%；
C7, it is that the obtained emulsion of 100 parts of b5, the mill base material that mass fraction is 50 parts, mass fraction are 500 parts by mass fraction
Deionized water mixing, obtain environment-friendlywater-based water-based paint；
C8, the water paint obtained on substrate using b7 is subjected to application to it, toasted after application in 170 DEG C of baking oven
30min, obtains the coated film c that thickness is 22 microns.
Environment-friendly type antimildew and antibacterial the coated film a, b, c that case study on implementation is obtained carry out fungus-proof test.
（1）Anti-microbial property test:
Nutrient agar is configured to the aqueous solution of mass fraction 3.5% with distilled water, autoclaving is poured into flat board training
Support in ware and prepare solid medium, the staphylococcus aureus and Escherichia coli after activation are inoculated in plating medium respectively,
The concentration of inoculated bacteria is 200/plate.By coated film a, b, c cuts a part, is placed on the surface of the flat board containing bacterium, 37 DEG C of cultures
24h, observes fungistatic effect, measures the diameter of inhibition zone.
Obtained result is：A in case study on implementation, b, c coated film are all substantially big to the antibacterial circle diameter of above-mentioned four kinds of bacterium
In 15mm, when being more than 15mm according to standard antibacterial circle diameter, illustrate that now material is extremely sensitive to bacterium, that is, illustrates the present invention
The mould proof coated film prepared has played its antibiotic property.
（2）Mould proof experiment:
By cultured black-koji mould, aspergillus terreus, aureobasidium pullulans, paecilomyces varioti bacterium, penicillium funiculosum, Trichoderma viride
Spore suspension is made in 6 kinds of strains such as bacterium, is mixed into mould medium.
By coated film a, b, c is placed on culture dish surface, and coated film is sprayed on by mould uniform suspension is fine and closely woven with sprayer
On, after slightly drying, cover ware lid.Culture dish is inverted after 3 days, 30 DEG C of cultures, and anti-mold effect is observed after 7 days.
| Sample | Dry film mould breeding potential | Dry film algae reproduction rate |
| a | 1/0 | 0/A |
| b | 0/0 | 1/B |
| c | 0/A | 1/0 |
According to BS 3900-G6 standards, it is to be less than 1%, 2 without growth, 1 to grow area that mould breeding potential, which is divided into 6 grades, i.e., 0,
It is 1-10% to grow area, 3 be that growth area is 11-30%, and 4 be that growth area is 31-70%, and 5 are more than 70% to grow area.
Density is divided into：0 is that, without growth, A is atomic, and B is slight, and C is moderate, and D is intensive.
From above-mentioned fungus-proof test, it can be found that the mould proof coating paper that case study on implementation is obtained can be effectively accomplished antimildew and antibacterial
Effect.
A kind of preparation method of environment-friendly type antimildew and antibacterial coated film in the embodiment that the present invention is provided, the coating of preparation
Film can effective antimildew and antibacterial, and the coated film is based on water paint, environmental protection, and with excellent corrosion resistance, good
Weatherability, scratch-resistant.
Presented above is only the preferred embodiment of the present invention, it is noted that to those skilled in the art, not
On the premise of departing from the invention design, various modifications and improvements can be made, these also should be regarded as the protection model of invention
Within enclosing.
Claims (8)
1. a kind of preparation method of environment-friendly type antimildew and antibacterial coated film, it is characterised in that comprise the steps of：
Sulfamic acid, 60-68 DEG C point of temperature are added after A1, in a kettle. addition modified epoxy, curing agent, stirring 1h
1-2h is dissipated, modified silicasol is added, vacuum distillation after deionized water, emulsification 30-50min is eventually adding and removes having in emulsion
Machine solvent, obtains the emulsion that solid content is 30-60%；
A2, it is that the obtained emulsion of 100 parts of A1, the mill base material that mass fraction is 50 parts, mass fraction are 200- by mass fraction
500 parts of deionized water mixing, obtains environment-friendlywater-based water-based paint；
A3, the water paint obtained on substrate using A2 carry out application to it, are toasted after application in 120-170 DEG C of baking oven
20-30min, film thickness monitoring is at 18-22 microns.
2. the preparation method of a kind of environment-friendly type antimildew and antibacterial coated film according to claim 1, it is characterised in that described
The preparation method of modified epoxy is：It is 20-50 parts of rings by novolac epoxy resin that mass fraction is 100 parts, mass fraction
Oxygen tree fat and mass fraction mix for 1-10 parts of chain extender, add catalyst, are carried out in reaction temperature at 150 DEG C -180 DEG C anti-
Should, when epoxide equivalent reaches 1000-2200g/mol, cool the temperature to 60-80 DEG C, be subsequently added organic amine compound, 90
Amination and chain extending reaction are carried out between DEG C -110 DEG C, the modified epoxy is obtained.
3. a kind of preparation method of environment-friendly type antimildew and antibacterial coated film according to claim 2, it is characterised in that the phenol
Formaldehyde epoxy resin includes times of phenol type novolac epoxy resin, orthoresol type novolac epoxy resin, bisphenol A-type novolac epoxy resin
Meaning is one or more；
The epoxy resin includes bisphenol A type epoxy resin, bisphenol-s epoxy resin, bisphenol f type epoxy resin, polyethylene glycol
Any one or more of diglycidyl ether and polypropylene glycol diglycidyl ether；
The chain extender includes single phenol, bisphenol compound, bisphenol A-type PPG, dicarboxylic acids, PPG, two
Any one or more in first mercapto alcohol；
The catalyst includes triethanolamine, triethylamine, diethylamine, triphenyl phosphorus, tri-phenyl-phosphorus bromide, dimethyl benzylamine, miaow
Any one or more in azoles, methylimidazole, 2- ethyl 4-methylimidazoles；
The organic amine compound includes butylamine, diethylamine, methyl butyl amine, MEA, diethanol amine, N- methyl ethanols
Any one or more in amine, 1,3- dimethyl propylamines, N, N- dimethyl ethanols amino acid salt or kitimine organic amine.
4. the preparation method of a kind of environment-friendly type antimildew and antibacterial coated film according to claim 1, it is characterised in that described solid
Agent includes any one or more during vinyl triamine, aminoethyl piperazine, m-phenylene diamine (MPD), diamino-diphenyl are added.
5. the preparation method of a kind of environment-friendly type antimildew and antibacterial coated film according to claim 1, it is characterised in that described to change
The preparation method of property Ludox comprises the following steps：
B1, with uniform particle sizes, size 20-40nm, proportion is used as crystal seed, 10-15 for 1.10-1.15 alkaline silicon dioxide colloidal sol
Times deionized water is diluted, and it is 10-12 to adjust pH value by mass fraction 4-6% potassium hydroxide solutions；Gained mixed liquor is carried out
Heating, temperature control is continuously added into proportion for 1.00-1.04 in 100-105 DEG C, heating process, and pH value is 2.0-3.0 silicon
Acid, to maintain liquid level constant；
B2, by molar fraction be 0.1-1% meta-aluminic acids, pass through dispersed with stirring to mass fraction be 5-10% NaOH and triethanolamine
Mixed solution in, and during the course of the reaction, the mixed solution containing aluminium described in 50-100ml was added every 1-3 hours, to maintain
The pH of reaction solution is between 9.0-10.0；
B3, by the reaction solution continuous heating time it is 50-60h, when the silicon dioxide gel proportion is reached 1.250-1.300, stops
Heating, reaction terminates, and finally obtains pH for 9.0-9.8, and particle diameter is 100-120nm modified silicasol.
6. a kind of preparation method of environment-friendly type antimildew and antibacterial coated film according to claim 1, it is characterised in that the color
The preparation method of slurry is：It is 10-20 parts to add epoxy resin, mass fraction that mass fraction is 100 parts in a kettle.
Titanium oxide, the kaolin of 20-25 parts of mass fraction, the carbon black that mass fraction is 1-5 parts and mass fraction are 200-300 parts and gone
Ionized water, is sanded after 10-15h after being well mixed with ball mill, obtains the mill base material that solid content is 40-60%.
7. a kind of preparation method of environment-friendly type antimildew and antibacterial coated film according to claim 1, it is characterised in that the base
Plate be metal, glass, natural resin, synthetic resin, ceramics, timber, paper, fiber, non-woven fabrics, weave cotton cloth or one kind in leather or
It is a variety of.
8. a kind of preparation method of environment-friendly type antimildew and antibacterial coated film, it is characterised in that comprise the steps of：
C1, be 100 parts of novolac epoxy resin by mass fraction, mass fraction is 20-50 parts of epoxy resin and mass fraction is
1-10 parts of chain extender mixing, adds catalyst, is reacted in reaction temperature at 150 DEG C -180 DEG C, when epoxide equivalent reaches
1000-2200g/mol, cools the temperature to 60-80 DEG C, is subsequently added organic amine compound, is carried out between 90 DEG C -110 DEG C
Amination and chain extending reaction, obtain the modified epoxy；
C2, with uniform particle sizes, size 20-40nm, proportion is used as crystal seed, 10-15 for 1.10-1.15 alkaline silicon dioxide colloidal sol
Times deionized water is diluted, and it is 10-12 to adjust pH value by mass fraction 4-6% potassium hydroxide solutions；Gained mixed liquor is carried out
Heating, temperature control is continuously added into proportion for 1.00-1.04 in 100-105 DEG C, heating process, and pH value is 2.0-3.0 silicon
Acid, to maintain liquid level constant；
C3, by molar fraction be 0.1-1% meta-aluminic acids, pass through dispersed with stirring to mass fraction be 5-10% NaOH and triethanolamine
Mixed solution in, and during the course of the reaction, the mixed solution containing aluminium described in 50-100ml was added every 1-3 hours, to maintain
The pH of reaction solution is between 9.0-10.0；
C4, by the reaction solution continuous heating time it is 50-60h, when the silicon dioxide gel proportion is reached 1.250-1.300, stops
Heating, reaction terminates, and finally obtains pH for 9.0-9.8, and particle diameter is 100-120nm modified silicasol；
Sulfamic acid, 60-68 DEG C point of temperature are added after C5, in a kettle. addition modified epoxy, curing agent, stirring 1h
1-2h is dissipated, modified silicasol is added, vacuum distillation after deionized water, emulsification 30-50min is eventually adding and removes having in emulsion
Machine solvent, obtains the emulsion that solid content is 30-60%；
C6, in a kettle. the addition titanium oxide that mass fraction is 100 parts of epoxy resin, mass fraction is 10-20 parts, quality
The kaolin that 20-25 part of number, the carbon black that mass fraction is 1-5 parts and the deionized water that mass fraction is 200-300 parts, mixing
It is sanded after uniform with ball mill after 10-15h, obtains the mill base material that solid content is 40-60%；
C7, it is that the obtained emulsion of 100 parts of C5, the mill base material that mass fraction is 50 parts, mass fraction are 200- by mass fraction
500 parts of deionized water mixing, obtains environment-friendlywater-based water-based paint；
C8, the water paint obtained on substrate using C7 carry out application to it, are toasted after application in 120-170 DEG C of baking oven
20-30min, film thickness monitoring is at 18-22 microns.
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| CN107868553A (en) * | 2017-11-21 | 2018-04-03 | 常州市鼎升环保科技有限公司 | A kind of preparation method of antimildew and antibacterial emulsion paint |
| CN108383230A (en) * | 2018-03-30 | 2018-08-10 | 海安县中丽化工材料有限公司 | A kind of water treatment agent |
| CN108408794A (en) * | 2018-03-30 | 2018-08-17 | 海安县中丽化工材料有限公司 | A kind of preparation method of water treatment agent |
| CN108456464A (en) * | 2018-02-07 | 2018-08-28 | 合肥达户电线电缆科技有限公司 | A kind of preparation method of new type environment friendly coating |
| CN109897528A (en) * | 2019-02-14 | 2019-06-18 | 安庆北化大科技园有限公司 | A kind of modified coating and the preparation method and application thereof |
| CN110093781A (en) * | 2019-05-22 | 2019-08-06 | 无锡风鹏新材料科技有限公司 | A kind of Environmental-protecting dust-removing adhesive rag and preparation method thereof |
| CN110732329A (en) * | 2018-07-20 | 2020-01-31 | 国家能源投资集团有限责任公司 | Silica sol containing potassium and preparation method thereof, iron-based Fischer-Tropsch synthesis catalyst and preparation method thereof, and Fischer-Tropsch synthesis method |
| CN117285257A (en) * | 2023-08-16 | 2023-12-26 | 浙江长兴杭华玻璃有限公司 | Production process of corrosion-resistant cosmetic glass bottle |
| RU2816683C1 (en) * | 2023-10-09 | 2024-04-03 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Российский химико-технологический университет имени Д. И. Менделеева (РХТУ им. Д. И. Менделеева) | Epoxy composition with antifungal action |
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| CN108456464A (en) * | 2018-02-07 | 2018-08-28 | 合肥达户电线电缆科技有限公司 | A kind of preparation method of new type environment friendly coating |
| CN108383230A (en) * | 2018-03-30 | 2018-08-10 | 海安县中丽化工材料有限公司 | A kind of water treatment agent |
| CN108408794A (en) * | 2018-03-30 | 2018-08-17 | 海安县中丽化工材料有限公司 | A kind of preparation method of water treatment agent |
| CN110732329A (en) * | 2018-07-20 | 2020-01-31 | 国家能源投资集团有限责任公司 | Silica sol containing potassium and preparation method thereof, iron-based Fischer-Tropsch synthesis catalyst and preparation method thereof, and Fischer-Tropsch synthesis method |
| CN110732329B (en) * | 2018-07-20 | 2022-12-27 | 国家能源投资集团有限责任公司 | Silica sol containing potassium and preparation method thereof, iron-based Fischer-Tropsch synthesis catalyst and preparation method thereof, and Fischer-Tropsch synthesis method |
| CN109897528A (en) * | 2019-02-14 | 2019-06-18 | 安庆北化大科技园有限公司 | A kind of modified coating and the preparation method and application thereof |
| CN110093781A (en) * | 2019-05-22 | 2019-08-06 | 无锡风鹏新材料科技有限公司 | A kind of Environmental-protecting dust-removing adhesive rag and preparation method thereof |
| CN110093781B (en) * | 2019-05-22 | 2022-02-22 | 无锡风鹏新材料科技有限公司 | Environment-friendly dust-removing adhesive wiping cloth and preparation method thereof |
| CN117285257A (en) * | 2023-08-16 | 2023-12-26 | 浙江长兴杭华玻璃有限公司 | Production process of corrosion-resistant cosmetic glass bottle |
| RU2816683C1 (en) * | 2023-10-09 | 2024-04-03 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Российский химико-технологический университет имени Д. И. Менделеева (РХТУ им. Д. И. Менделеева) | Epoxy composition with antifungal action |
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