CN101955697A - Ceramic non-stick coating with bacteriostasis action and coating method thereof - Google Patents
Ceramic non-stick coating with bacteriostasis action and coating method thereof Download PDFInfo
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Abstract
The invention belongs to the process technology field of coating liquid or other fluid on the surface, in particular to a ceramic non-stick coating with the bacteriostasis action. The coating is formed by mixing a component (A), a component (B) and a component (C) in a weight ratio of 2 to 0.5-2 to 0.1-2, wherein the component (A) is prepared by dispersing and grinding the following components in percentage by weight: 50-100 percent of silica sol, 0-50 percent of temperature-resisting pigment, 0-20 percent of inert pigment, 0-2 percent of dispersing aid and 0-2 percent of leveling aid for more than 2 h; the component (B) is prepared by mixing the following components in percentage by mass:0.2-1.5 percent of acetic acid and the balance of at least one silane; and the component (C) is prepared by dispersing and dissolving the following components in percent by mass of 1-10 percent of alcohol-soluble acrylic resin, 0-30 percent of non-stick agent and 1-50 percent of antibacterial material in 50-95 percent of isopropanol. Compared with a traditional non-stick coating, the non-stick coating without being added with substances, such as PTFE (Polytetrafluoroethylene), PFOA (Perfluorooctanoic Acid), and the like is environment-friendly and safe and has the bacteriostasis and sterilization functions.
Description
Technical field
The invention belongs to surperficial coating liquid or other fluidic Technology field, relate to a kind of non-sticky metallic coating, specifically a kind of ceramic non-stick coating with bacteriostatic action.
Background technology
Non-sticky metallic coating was developed rapidly later by the invention application in 1958, was widely used in fields such as cooker, small household appliances, and it is convenient to have brought to people's life.But its nucleus of existing non-sticky metallic coating is a polytetrafluoroethylene (PTFE), and tetrafluoroethylene can add denier ammonium perfluorocaprylate (PFOA) in production process, after the PFOA that chemical property is stable enters physical environment and human body, meeting long-term existence, rather than very fast decomposition.Studies show that low dosage PFOA not only appears in river, ocean and the soil, also be present in people's the blood, and in experimentation on animals, be proved carcinogenesis and other adverse consequencess.For this reason, USEPA (EPA) requires tetrafluoroethylene manufacturers to use minimizing to stop to produce PFOA in 95%, 2015 year at PFOA in 2010.Discover that in addition existing non-sticky metallic coating is surpassing under the high temperature more than 260 ℃, tetrafluoroethylene can discharge obnoxious flavour, causes to the pollution of environment with to the injury of human body.
The patent ZL 02807868.3 of E. I. Du Pont de Nemours and Co has introduced a kind of fluoropolymer non-sticky metallic coating, make coating have wear resistance and food to peel off both and show all good characteristics by adding ceramic particle, improve the work-ing life of non-sticky metallic coating greatly, but this non-sticky metallic coating main raw is a fluoropolymer, high temperature (more than 260 ℃) can discharge harmful resolvent, and generally can use this hazardous material of PFOA in the production process, so its application is subjected to certain limitation.Because non-sticky metallic coating is mainly used on the non-sticking cooking utensils, frequently contact with food, and food and non-sticking cooking utensils unavoidably has various unwanted bacterias, influence the healthy of people.Therefore, need a kind of ceramic non-stick coating that had not only had bacteriostatic action but also do not contained or contain micro-objectionable impurities of development to satisfy the demand of people to non-sticky metallic coating.
Summary of the invention
The defective that the present invention is directed to prior art provides a kind of ceramic non-stick coating with bacteriostatic action, and this non-sticky metallic coating does not add material, Environmental Safety such as PTFE and PFOA, has the restraining and sterilizing bacteria function simultaneously.
Another object of the present invention provides a kind of coating method of this ceramic non-stick coating.
Above-mentioned technical problem of the present invention is implemented by the following technical programs:
A kind of ceramic non-stick coating with bacteriostatic action, this coating are to be mixed by weight 2:0.5～2:0.1～2 by A, B, C three components, wherein:
A component: will be by the component of massfraction: silicon sol 50～100%, heatproof pigment 0～50%, pigment extender 0～20%, dispersing auxiliary 0～2% and leveling auxiliary agent 0～2% disperse, and grind then and obtain the A component more than 2 hours;
B component: will be that at least a silane mixture forms by the acetate 0.4～1.5% and the surplus of massfraction;
The C component: will in Virahol 50～95%, obtain the C component by the pure soluble acrylic resin 1～10% of massfraction, sticking auxiliary agent 0～30% and antibacterial material 1～50% dispersing and dissolving, and the addition of described antibacterial material be in A, B, C three components solid ingredient total mass 1～25%.
Silicon sol
Silicon sol is the dispersion liquid of nano level silica dioxide granule in water or in the solvent.Because the SiO in the silicon sol
2Silicon sol contains a large amount of water and hydroxyl, so also can be expressed as SiO
2NH
2O.Silicon sol as the silane condensation dehydration of one of inorganic filming substance matter and hydrolysis, obtains SiO in the present invention
2Reticulated structure, thus make non-sticky metallic coating have performances such as hardness, water tolerance, erosion resistance and temperature tolerance.
Silicon sol among the present invention, pH are 2-11, and particle diameter is 5-50nm, and dioxide-containing silica is 20-50%.In the present invention, the massfraction of silicon sol in the A component is 50-100%.
Heatproof pigment
In the present invention, heatproof pigment uses as tinting material.Heatproof pigment among the present invention is nontoxic pigment dyestuff and/or the mineral dye of heatproof more than 200 ℃, can detect by ROHS, include but not limited to: rutile titanium white, titan yellow, iron oxide black, red iron oxide, cobalt black, cobalt blue, cobalt green, carbon black, pearly-lustre and aluminium silver powder etc.
In the present invention, the massfraction of heatproof pigment in the A component is 0-50%.
Pigment extender
In the present invention, pigment extender adds as filler, helps non-sticky metallic coating to improve solids content, improves the non-sticky metallic coating operability, can also improve the intensity of non-sticky metallic coating in addition.
Pigment extender among the present invention is that heatproof is nontoxic, particle diameter is less than the powder filler of 100 μ m, be selected from inorganic materials materials such as whisker class, fiber-like, ceramic particle, include but not limited to: silica powder, silicon wafer palpus, potassium titanate crystal whisker, aluminum oxide, diatomite, silicon carbide and diamond etc.
In the present invention, the massfraction of pigment extender in the A component is 0-20%.
Dispersing auxiliary
Dispersing auxiliary among the present invention is the coatings additive(s) that can help pigment and fillers dispersed, for example German BYK-190.
In the present invention, the massfraction of dispersing auxiliary in the A component is 0-2%.
Leveling auxiliary agent
Leveling auxiliary agent among the present invention is characterized in that helping the coatings additive(s) of the wetting levelling of coating, for example BYK-333.
In the present invention, the massfraction of leveling auxiliary agent in the A component is 0-2%.
Silane
Silane described in the present invention has following general molecular formula: R
nSi (OR ')
4-n,Wherein: R is alkyl, aryl, substituted alkyl or substituted aryl; R ' is C
1– C
5Alkyl; N=1,2 or 0.
Silane is used for being condensed into filmogen with silicon sol after the hydrolysis, and R requires the short great thermotolerance of chain, and R ' requires the short easy hydrolysis of chain.
In silane preferable methyl Trimethoxy silane of the present invention (MTMS), Union carbide A-162, phenyltrimethoxysila,e, phenyl triethoxysilane, tetraethyl silicate (TEOS) and the dimethyldiethoxysilane one or more.
Acetate
Acetate among the present invention, its effect are the silane hydrolyzate catalyzer, and addition is the 0.1-0.5% of A, B, C three component total amounts, and addition is excessive, and hydrolysis rate is too fast, reacts bad control, and addition is very low, and hydrolysis rate is slow excessively, and hydrolysis does not even take place.Acetate also can be used organic acid or mineral acid replacements such as formic acid, hydrochloric acid in the present invention.
Not sticking auxiliary agent
Not sticking auxiliary agent among the present invention, its effect is to improve the smooth and reduction non-sticky metallic coating surface tension in non-sticky metallic coating surface, make non-sticky metallic coating cannot not have stickingly and performance easy to clean, for example the model of DOWCORNING company is the release not silicone oil of sticking effect of having of 1-9770.
The not sticking weight ratio of additive dosage in the C component is 0-30%, at the 0-2.5% of A, B, C three component gross weights.
Antibacterial material
Antibacterial material is to make the growth of certain micro-organisms (bacterium, fungi, yeast, algae and virus etc.) or breeding remain on chemical substance necessary below horizontal within a certain period of time.
The easy hydrolysis of general organic antibacterial agent, heat-resisting poor, in water, easily to separate out, validity period is short, is not suitable for being used in the non-sticky metallic coating; Though energy such as inorganic antiseptic mercury, cadmium, lead heatproof is high and have bacteria resistance function, but heavy metal material is harmful, also is not suitable for using in non-sticky metallic coating.
Antibacterial material among the present invention is for having strong bacteria resistance function and material nontoxic, heatproof.Antibacterial material of the present invention is selected from nanometer silver, zircomium-tiatnium phosphate silver, titanium dioxide silver permutoid etc., and addition is the 1-25% of solids content in A, B, the C three component gross weights.
The preferred antibacterial material of the present invention is a nanometer silver, and owing to the cost reason, addition is the 1-5% of solids content in A, B, the C three component gross weights.The nano silver antibacterial material all has intensive to suppress and killing action to tens of kinds of pathogenic microorganisms such as intestinal bacteria, gonococcus, chlamydia trachomatis, has strong, antibiotic lasting, the safety non-toxic of broad-spectrum antimicrobial, potent sterilization, perviousness and can not produce characteristic such as resistance.
The alcohol soluble acrylic resin
Pure soluble acrylic resin among the present invention belongs to organic composition, can assist the inorganic paint film forming effectively, and prevent to film and cause film cracking because internal stress is excessive, but its temperature tolerance is poor comparatively speaking, so addition is unsuitable excessive, general addition is the 1-10% of C component, the 0.5-1.5% of A, B, C three component gross weights.
Virahol
Virahol is as solvent, and dissolving disperses not sticking auxiliary agent, antibacterial material and pure soluble acrylic resin.
As preferably, the weight ratio of described A, B, C three components is 2:1:0.1～1.
As preferably, in the A component, the pH of described silicon sol is 2～11, and particle diameter is 5～50nm, and dioxide-containing silica is 20～50%.
As preferably, in the A component, described heatproof pigment is nontoxic pigment dyestuff and/or the mineral dye of heatproof more than 200 ℃, is selected from rutile titanium white, titan yellow, iron oxide black, red iron oxide, cobalt black, cobalt blue, cobalt green, carbon black, pearly-lustre and the aluminium silver powder one or more.
As preferably, described pigment extender is the nontoxic particle diameter powder filler less than 100 μ m, is selected from silica powder, silicon wafer palpus, potassium titanate crystal whisker, aluminum oxide, diatomite, silicon carbide and the diamond one or more.
As preferably, described dispersing auxiliary is BYK-190; Described leveling auxiliary agent is BYK-333.
As preferably, in the B component, described silane has following general molecular formula: R
nSi (OR ')
4-n, wherein: R is alkyl, aryl, substituted alkyl or substituted aryl; R ' is C
1– C
5Alkyl; N=1,2 or 0.
As preferably, in the B component, the addition of described acetate is 0.1～0.5% of A, B, C three component gross weights.
As preferably, in the C component, described sticking auxiliary agent is to have the release silicone oil of sticking effect, and the present invention adopts is that the model of DOW CORNING (Dowcorning) company is the silicone oil of 1-9770.
As preferably, in the C component, described antibacterial material is selected from nanometer silver, zircomium-tiatnium phosphate silver and titanium dioxide silver permutoid.
A kind of coating method of described ceramic non-stick coating, this method may further comprise the steps:
A, pre-treatment: the metal base sandblast is made its surface irregularity, to increase the adherence of coating;
B, coating mixes: the A described in will inventing, B component stir or roll 3～15 hours (according to the different curing time differences of temperature) by weight mixing, and the condensation reaction that is hydrolyzed adds the C component then and mixes;
C, paint spay-coating: will be preheating to 40～80 ℃ (can determine preheating temperature) through the base material after a step process according to practical situation, the coating that step b is obtained by compressed air spraying on the base material of preheating;
D, sintering curing: the base material levelling oven dry 10min under 55～80 ℃ of temperature with the c step obtains, be warmed up to 280 ℃～300 ℃ more gradually, sintering 10min postcooling gets final product.
Compare with existing non-sticky metallic coating, the ceramic non-stick coating with bacteriostatic action of the present invention belongs to inorganic paint, and heatproof is more than 300 ℃, do not add materials such as PTFE and PFOA in the production process, Environmental Safety owing to add antibacterial material, therefore has the restraining and sterilizing bacteria function simultaneously.Thereby the present invention can be widely used in obtaining having on cooker and other kitchen tools surfaces function cooker or other products of bacteriostasis efficacy.The experiment proved that the cooker that applies ceramic non-stick coating of the present invention has antibacterial or germ-resistant effect, can reach the purpose of food sterilization and food fresh-keeping, people's is healthy thereby protected.
Embodiment
Below be specific embodiments of the invention, these embodiment can do further to replenish and explanation to the present invention.For convenient test, heatproof pigment is selected the titanium white R-900 of E.I.Du Pont Company for use in the embodiment of the invention, and pigment extender is selected the aluminum oxide of 5 micron grain sizes for use, and silicon sol is selected the SNOWTEX-0 of Nissan for use, but the present invention is not limited to these embodiment.
The coating method of ceramic non-stick coating of the present invention is specific as follows: a, pre-treatment: the metal base sandblast is made its surface irregularity, to increase the adherence of coating; B, coating mixes: the A described in the present invention, B component are stirred or roll 3～15 hours (according to the different curing time differences of temperature) by weight mixing, and the condensation reaction that is hydrolyzed adds the C component then and mixes; C, paint spay-coating: will be preheating to 40～80 ℃ through the base material after a step process, can determine preheating temperature according to practical situation here, with coating by compressed air spraying on the base material of preheating; D, sintering curing: the base material levelling oven dry 10min under 55～80 ℃ of temperature with the c step obtains, be warmed up to 280 ℃～300 ℃ more gradually, sintering 10min postcooling gets final product.
Employed technology in following examples unless stated otherwise, is routine techniques known to those skilled in the art; Employed plant and instrument, reagent etc., only this specification sheets specifies, is that the research of this area and technician can be by public approach acquisition.
Embodiment 1-8:
The coating method of ceramic non-stick coating of the present invention is specific as follows:
A, pre-treatment: the metal base sandblast is made its surface irregularity, to increase the adherence of coating;
B, coating mix: the A in the table 1, B component were stirred 6～7 hours by weight mixing, make the reactant condensation reaction that is hydrolyzed, add the C component then and mix;
C, paint spay-coating: will be preheating to 50～60 ℃ through the base material after a step process, with coating by compressed air spraying on the base material of preheating;
D, sintering curing: the base material levelling oven dry 10min under 55～70 ℃ of temperature with the c step obtains, be warmed up to 280 ℃～300 ℃ more gradually, sintering 10min postcooling gets final product.
Embodiment 9-16:
The coating method of ceramic non-stick coating of the present invention is specific as follows:
A, pre-treatment: the metal base sandblast is made its surface irregularity, to increase the adherence of coating;
B, coating mix: A, the B component that will continue in the table 1 were rolled 8～9 hours by weight mixing, and made the reactant condensation reaction that is hydrolyzed, and added the C component then and mixed;
C, paint spay-coating: will be preheating to 60～80 ℃ through the base material after a step process, with coating by compressed air spraying on the base material of preheating;
D, sintering curing: the base material levelling oven dry 10min under 70～80 ℃ of temperature with the c step obtains, be warmed up to 280 ℃～300 ℃ more gradually, sintering 10min postcooling gets final product.
Table 1 (unit: g)
Continuous table 1 (unit: g)
Material in the table 1 is specially:
(1) silicon sol---the SNOWTEX-0 of Nissan;
(2) heatproof pigment---the titanium white R900 of E.I.Du Pont Company;
(3) pigment extender---the aluminum oxide of 5 micron grain sizes;
(4) not sticking auxiliary agent---the 1-9770 of Dow Corning Corporation (DOWCORNING) silicone oil;
(5) antibacterial material---nanometer silver, zircomium-tiatnium phosphate silver or titanium dioxide silver.
Table 2 detected result
Continuous table 2 detected result
Test method in the table 2 is specially:
Pencil hardness: test Chinese pencil hardness, GB/T 6739;
The thickness of filming: film thickness gauge, GB/T 13452.2-1992
Gloss: 60 ° of glossmeters, JIS K 6893-1995;
Sticking power: 2mm * 2mm, grid, 100/100,3M adhesive tape 10 times, JIS K 6894-1996;
Film cracking: 80 times of magnifying glasses are observed the film cracking situation
Alkali resistance: 5% aqueous sodium carbonate soaked 24 hours, and JIS K 5,600 8.21;
Acid resistance: 5% aqueous sulfuric acid soaked 24 hours, and JIS K 5,600 8.22;
Resistance to salt water: 5% sodium chloride aqueous solution soaked 240 hours, and JIS K 5,600 8.23;
Solvent-resisting: MEK solvent 1 kgf wiping 100 times back and forth;
Thermotolerance: 300 ℃ of constant temperature 24 hours, observe aberration and change, JIS K 5,400 8.13;
Viscosity not: 170 ± 10 ℃ of fried egg, BS 7069:1988;
Antibacterial parameter: Japanese JIS Z 2801:2000 test method, Log value of antimicrobial activity 〉=2 meet the requirements;
PFOA:SGS detects PFOA content;
Whether PTFE:SGS detects the PTFE material and adds.
The foregoing description is base materials employed to be aluminium alloy 20.0mm * 12.0mm * 3.2mm (long * wide * thick).
Can clearly find out from the foregoing description, the addition of nanometer silver is at A, B, 1% of solids content when following in the C three component gross weights, its bacteriostatic effect (antibacterial parameter＜2) can not reach the standard (Log value of antimicrobial activity 〉=2) of Japanese JIS Z 2801:2000 test method, the addition of nanometer silver is at A, B, 5% of solids content when above in the C three component gross weights, the fine and cost increase of its fungistatic effect is so the addition of nanometer silver is at A, B, 1%～5% of solids content relatively is fit to the present invention in the C three component gross weights.Can it is evident that from embodiment the fungistatic effect of antibacterial material is that nanometer silver is better than zircomium-tiatnium phosphate silver and titanium dioxide silver greatly in addition, so the preferred nanometer silver of the antibacterial material of the present invention; This coating is not used materials such as PTFE and PFOA, Environmental Safety simultaneously.
Specific embodiment described in the present invention only is that the present invention's spirit is illustrated.The technician of the technical field of the invention can make various modifications or replenishes or adopt similar mode to substitute described specific embodiment, but can't depart from spirit of the present invention or surmount the defined scope of appended claims.Although the present invention has been made detailed explanation and has quoted some specific exampless as proof, to those skilled in the art, only otherwise leave that the spirit and scope of the present invention can be done various variations or correction is obvious.
Claims (10)
1. the ceramic non-stick coating with bacteriostatic action is characterized in that this coating is to be mixed by weight 2:0.5～2:0.1～2 by A, B, C three components, wherein:
A component: will be by the component of massfraction: silicon sol 50～100%, heatproof pigment 0～50%, pigment extender 0～20%, dispersing auxiliary 0～2% and leveling auxiliary agent 0～2% disperse, and grind then and obtain the A component more than 2 hours;
B component: will be that at least a silane mixture forms by the acetate 0.4～1.5% and the surplus of massfraction;
The C component: will in Virahol 50～95%, obtain the C component by the pure soluble acrylic resin 1～10% of massfraction, sticking auxiliary agent 0～30% and antibacterial material 1～50% dispersing and dissolving, and the addition of described antibacterial material be in A, B, C three components solid ingredient total mass 1～25%.
2. ceramic non-stick coating according to claim 1 is characterized in that: in the A component, the pH of described silicon sol is 2～11, and particle diameter is 5～50nm, and dioxide-containing silica is 20～50%.
3. ceramic non-stick coating according to claim 1, it is characterized in that: in the A component, described heatproof pigment is selected from one or more in rutile, titanium white, titan yellow, iron oxide black, red iron oxide, cobalt black, cobalt blue, cobalt green, carbon black, pearly-lustre and the aluminium silver powder; Described pigment extender is the powder filler of particle diameter less than 100 μ m, is selected from silica powder, silicon wafer palpus, potassium titanate crystal whisker, aluminum oxide, diatomite, silicon carbide and the diamond one or more; Described dispersing auxiliary is BYK-190; Described leveling auxiliary agent is BYK-333.
4. according to claim 1 or 2 or 3 described ceramic non-stick coatings, it is characterized in that: in the B component, described silane has following general molecular formula: R
nSi (OR ')
4-n, wherein: R is alkyl, aryl, substituted alkyl or substituted aryl; R ' is C
1– C
5Alkyl; N=1,2 or 0.
5. according to claim 1 or 2 or 3 described ceramic non-stick coatings, it is characterized in that: in the B component, the addition of described acetate is 0.1～0.5% of A, B, C three component gross weights.
6. according to claim 1 or 2 or 3 described ceramic non-stick coatings, it is characterized in that: in the C component, described not sticking auxiliary agent is silicone oil 1-9770.
7. according to claim 1 or 2 or 3 described ceramic non-stick coatings, it is characterized in that: in the C component, described antibacterial material is selected from a kind of in nanometer silver, silver ions, zircomium-tiatnium phosphate silver and the titanium dioxide silver permutoid.
8. according to claim 1 or 2 or 3 described ceramic non-stick coatings, it is characterized in that: the weight ratio of described A, B, C three components is 2:1:0.1～1.
9. ceramic non-stick coating according to claim 4 is characterized in that: the weight ratio of described A, B, C three components is 2:1:0.1～1.
10. the coating method of a ceramic non-stick coating as claimed in claim 1, this method may further comprise the steps:
A, pre-treatment: the metal base sandblast is made its surface irregularity;
B, coating mixes: by weight mixing stirring or rolling 3～15 hours, the condensation reaction that is hydrolyzed adds the C component then and mixes with the A in the claim 1, B component;
C, paint spay-coating: will be preheating to 40～80 ℃ through the base material after a step process, the paint spay-coating that step b is obtained is on the base material of preheating;
D, sintering curing: the base material levelling oven dry 10min under 55～80 ℃ of temperature with the c step obtains, be warmed up to 280 ℃～300 ℃ more gradually, sintering 10min postcooling gets final product.
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