CN114605888A - Anti-mildew type transparent fireproof coating and preparation method thereof - Google Patents
Anti-mildew type transparent fireproof coating and preparation method thereof 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
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09D161/32—Modified amine-aldehyde condensates
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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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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
- C09D5/185—Intumescent paints
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/327—Aluminium phosphate
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- 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
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- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Abstract
The invention discloses an anti-mildew type transparent fireproof coating, which comprises the following solutes in percentage by mass: 6 percent of methylated melamine formaldehyde resin, 34 percent of polyvinyl alcohol phosphate, 1.2 percent of nano titanium dioxide silver-loaded or 0.5 percent of nano silicon dioxide aluminum silver-loaded, and the balance of aluminum dihydrogen phosphate; according to the invention, polyvinyl alcohol phosphate and aluminum dihydrogen phosphate are compounded to obtain an organic-inorganic composite flame-retardant system, the organic-inorganic composite flame-retardant system and methylated melamine formaldehyde resin are blended to prepare the transparent fireproof coating, and nano silver-loaded particles are further introduced as an antibacterial agent in a physical blending manner to prepare the antifungal type transparent fireproof coating, so that the current situation of simplification of the function of the coating is broken, and the prepared antifungal type transparent fireproof coating has excellent transparency, flame retardance, antibacterial property and flexibility, is simple in composition and preparation process, and is beneficial to industrial production.
Description
Technical Field
The invention belongs to the technical field of fireproof coatings, and particularly relates to an anti-mildew type transparent fireproof coating and a preparation method thereof.
Background
The mildew-resistant transparent fireproof coating integrates fire prevention and mildew prevention, can effectively prevent wood from mildewing, can also play a role in protecting a base material when a fire disaster occurs, and is suitable for fire prevention and mildew prevention protection of wood structure buildings.
Patent document CN 105802436B discloses a nano intumescent transparent fire-retardant coating, which is obtained by compounding acid phosphate grafted with nano filler and a polycyanum amide resin. Patent document CN101050331A discloses a room temperature curing transparent intumescent flame retardant epoxy resin fire retardant coating, which is obtained by synthesizing an acid phosphate curing agent from phosphorus pentoxide, phosphoric acid and alcohol as raw materials and mixing the acid phosphate curing agent with epoxy resin in a ratio of 1: 1. However, the transparent fire-retardant coating disclosed in the above documents only has excellent fire-retardant properties and does not have mildew-resistant properties. Patent document CN10419450A discloses a nano fireproof coating, which improves the antibacterial performance of the coating by adding nano silica on the basis of ensuring the fireproof performance of the coating, but the nano silica is added in too much amount, and is only suitable for buildings and is not suitable for places with higher requirements on transparency.
Disclosure of Invention
In view of the above, the present invention aims to provide an anti-mold type transparent fireproof coating, which not only has excellent fireproof performance, but also has excellent mold resistance, and is simple in composition and preparation process, and beneficial to industrial production.
Through research, the invention provides the following technical scheme:
1. the anti-mildew type transparent fireproof coating comprises the following solutes in percentage by mass: 6 percent of methylated melamine formaldehyde resin, 34 percent of polyvinyl alcohol phosphate, 1.2 percent of nano titanium dioxide silver-loaded or 0.5 percent of nano silicon dioxide aluminum silver-loaded, and the balance of aluminum dihydrogen phosphate.
Namely, the solute of the anti-mildew type transparent fireproof coating comprises the following components in percentage by mass: 6 percent of methylated melamine formaldehyde resin, 34 percent of polyvinyl alcohol phosphate, 1.2 percent of nano titanium dioxide silver-carrying and 58.8 percent of aluminum dihydrogen phosphate; or the solute of the anti-mildew transparent fireproof coating comprises the following components in percentage by mass: 6 percent of methylated melamine formaldehyde resin, 34 percent of polyvinyl alcohol phosphate, 0.5 percent of nano silicon dioxide aluminum silver and 59.5 percent of aluminum dihydrogen phosphate.
2. The preparation method of the anti-mildew type transparent fireproof coating comprises the following steps: adding the silver-loaded nano titanium dioxide or the silver-loaded nano silicon aluminum oxide into the aqueous solution of polyvinyl alcohol phosphate according to the proportion, uniformly stirring, then adding the aqueous solution of aluminum dihydrogen phosphate according to the proportion, and uniformly stirring to obtain a component A; taking a methylated melamine formaldehyde resin aqueous solution as a component B; and uniformly stirring the component A and the component B in proportion, and standing until no bubbles exist to obtain the mildew-resistant transparent fireproof coating.
The polyvinyl alcohol phosphate is a macromolecular flame retardant, can overcome the defect that a micromolecular phosphate flame retardant is easy to volatilize, improves the flame retardant stability, and can improve the flexibility of a coating because the polyvinyl alcohol phosphate contains a polyvinyl alcohol flexible chain segment. The aluminum dihydrogen phosphate is a flame retardant with the characteristics of high-temperature cohesiveness, high-temperature foaming and the like. The polyvinyl alcohol phosphate and the aluminum dihydrogen phosphate are compounded, so that the compounding of organic and inorganic flame retardants can be realized, and the defect of single flame retardant is overcome. According to the invention, polyvinyl alcohol phosphate and aluminum dihydrogen phosphate are compounded to obtain an organic-inorganic composite flame retardant system, and the organic-inorganic composite flame retardant system is blended with methylated melamine formaldehyde resin to obtain the transparent fireproof coating.
Nano TiO 22Ag is a novel photocatalytic type mildew-proof antibacterial agent and has the characteristics of high catalytic activity, stable chemical property, environmental friendliness and the like. Under the irradiation of ultraviolet light, the nano TiO2Ag generates electron-hole pairs with H on the surface2O molecule and O2The molecules form active hydroxyl and superoxide ions, which can destroy the self structure of bacteria to achieve the effect of sterilization. Under the conditions of weak light and darkness, Ag can improve the nano TiO2Photocatalytic activity, nano Ag also has antibacterial property, and nano TiO2Has synergistic antibacterial effect. Photocatalytic nano TiO2the-Ag antibacterial agent is uniformly dispersed into the transparent fireproof coating in a physical blending mode, so that the antibacterial transparent fireproof coating with both antibacterial performance and fireproof performance can be prepared.
Nano SiO 22-Al-Ag is prepared by physical adsorption method on porous nano SiO2The surface is loaded with silver and aluminum oxide, so that metal ions are firmly combined on SiO2The porous skeleton is not easy to fall off. The photocatalysis type nano SiO2the-Al-Ag antibacterial powder is uniformly dispersed into the transparent fireproof coating in a physical blending mode, so that the coating has excellent antibacterial performance and the fireproof performance is improved to a certain extent.
The invention has the beneficial effects that: according to the invention, polyvinyl alcohol phosphate and aluminum dihydrogen phosphate are compounded to obtain an organic-inorganic composite flame-retardant system, the organic-inorganic composite flame-retardant system and methylated melamine formaldehyde resin are blended to prepare the transparent fireproof coating, and nano silver-loaded particles are further introduced as an antibacterial agent in a physical blending manner to prepare the antifungal type transparent fireproof coating, so that the current situation of simplification of the function of the coating is broken, and the prepared antifungal type transparent fireproof coating has excellent transparency, flame retardance, antibacterial property and flexibility, is simple in composition and preparation process, and is beneficial to industrial production.
Drawings
FIG. 1 shows a coating layer containing nano TiO2Temperature profile of the back of the wood panel with an anti-mildew transparent fireproof coating of Ag.
FIG. 2 shows a coating layer containing nano TiO2-digital photo of carbon residue after board-like combustion of Ag anti-mildew type transparent fireproof coating.
FIG. 3 shows the case of no nano TiO2-MPPVA 0 of Ag and nano TiO containing2-SEM image of the surface of the carbon layer formed by thermal expansion of mpva 6 of Ag: (a) MPPVA 0500 times of images, (b) MPPVA 01000 times of images, (c) MPPVA 6500 times of images, and (d) MPPVA 61000 times of images.
FIG. 4 is an EDS-mapping image of nano-Ag and nano-Ti: (a) magnification of 20000, and (b) magnification of 50000.
FIG. 5 shows a coating layer containing nano SiO2Temperature rise curve of the back of the wood panel of an antimycotic transparent fireproof coating of-Al-Ag.
FIG. 6 shows a coating layer containing nano SiO2The wood board of the anti-mildew type transparent fireproof coating of-Al-Ag simulates a digital photo of carbon residue after burning by a large board method.
FIG. 7 shows the case of no nano SiO2MPPVA0 of-Al-Ag and nano SiO contained2-MPPVA 4 of Al-Ag SEM image of the surface of the carbon layer formed by thermal expansion: (a) MPPVA 0500 time image, (b) MPPVA 01000 time image, (c) MPPVA4500 time image, and (d) MPPVA 41000 time image.
FIG. 8 is an EDS-mapping image of nano Ag and nano Si: (a) the magnification is 20000, and (b) the magnification is 50000.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, preferred embodiments of the present invention are described in detail below.
Example 1 Nano-TiO containing2Preparation of anti-mildew transparent fireproof paint of-Ag
Proportionally mixing nano TiO2Adding Ag into the polyvinyl alcohol phosphate aqueous solution, uniformly stirring at room temperature, then adding aluminum dihydrogen phosphate aqueous solution according to a proportion, and uniformly stirring at room temperature to obtain a component A; taking a methylated melamine formaldehyde resin aqueous solution as a component B; mixing component A and component B at room temperature, standing in shade for 30-60min until no bubbles are formed to obtain the final product containing nanometer TiO2Ag, the solute formulation of which is shown in Table 1.
TABLE 1 Nano-TiO-containing2Solute formula (mass fraction) of anti-mildew transparent fireproof paint of Ag
| Sample(s) | Methylated melamine formaldehyde resin | Aluminium dihydrogen phosphate | Nano TiO 22-Ag | Polyvinyl alcohol phosphoric acid ester |
| MPPVA0 | 6％ | 60％ | 0 | 34％ |
| MPPVA1 | 6％ | 59.7％ | 0.3％ | 34％ |
| MPPVA2 | 6％ | 59.6％ | 0.4％ | 34％ |
| MPPVA3 | 6％ | 59.5％ | 0.5％ | 34％ |
| MPPVA4 | 6％ | 59.2％ | 0.8％ | 34％ |
| MPPVA5 | 6％ | 59.0％ | 1.0％ | 34％ |
| MPPVA6 | 6％ | 58.8％ | 1.2％ | 34％ |
| MPPVA7 | 6％ | 58.5％ | 1.5％ | 34％ |
Example 2 Nano-TiO containing2Characterization of the Properties of the antimycotic transparent fireproof coating of Ag
(1) Analysis of coating transparency
The nano TiO-containing material prepared in example 12The mildew-resistant transparent fireproof coating of Ag-MPPVA 0-MPPVA 7 is 500g/m2The coated glass sheets were respectively coated on transparent glass sheets of 50mm × 50mm × 3mm, and the transparency of the coating was measured using a light transmittance tester.
The results are shown in Table 2, without adding nano TiO2The transparent fireproof coating of Ag has the highest light transmittance MPPVA 0; associated with nano TiO2The transmittance of the coating gradually decreases as the amount of Ag added increases, because of the nano TiO2The refractive index of-Ag is different from that of methylated melamine formaldehyde resin, so that light scattering phenomenon can occur, the transparency of the coating is reduced, but when nano TiO is used2When the addition amount of the Ag is increased to 1.5 percent, the light transmittance of the coating can still reach 83.95 percent. And, will contain nano TiO2The Ag-containing mildew-resistant transparent fireproof coating MPPVA 0-MPPVA 7 is respectively coated on the surface of the plywood, the texture structure of the wood can still be clearly seen, the decorative performance of the wood is not influenced, and the condition shows that the wood contains nano TiO2The coating of the anti-mildew transparent fireproof paint of Ag still has good light transmissionCan be used.
TABLE 2 Nano-TiO containing2Coating transparency of anti-mildew type transparent fire-retardant coating of Ag
| Sample (I) | MPPVA0 | MPPVA1 | MPPVA2 | MPPVA3 |
| Degree of transparency/%) | 92.12 | 91.89 | 91.32 | 91.03 |
| Sample (I) | MPPVA4 | MPPVA5 | MPPVA6 | MPPVA7 |
| Degree of transparency/%) | 90.12 | 88.93 | 84.56 | 83.95 |
(2) Coating adhesion analysis
The nano TiO-containing paint film obtained in example 1 was tested by using a QFH-HD600 adhesion tester in accordance with GB/T9286-1998 test for marking paint and varnish films2The coating adhesion rating of the antimycotic transparent fireproof paint of Ag.
The results are shown in Table 3, the adhesive force grades of the coatings have no obvious difference and are all grade 2, and the requirements on the physical and chemical property adhesive force in the national standard of the finishing type fireproof coating are met.
TABLE 3 Nano-TiO containing2Coating adhesion rating of an anti-mildew transparent fire-retardant coating of Ag
| Sample (I) | MPPVA0 | MPPVA1 | MPPVA2 | MPPVA3 |
| Adhesion/grade | 2 | 2 | 2 | 2 |
| Sample (I) | MPPVA4 | MPPVA5 | MPPVA6 | MPPVA7 |
| Adhesion/grade | 2 | 2 | 2 | 2 |
(3) Analysis of coating fire behavior
Simulating a large-plate combustion method: the nano TiO-containing material prepared in example 12The mildew-resistant transparent fireproof coating of Ag-MPPVA 0-MPPVA 7 is 500g/m2The coating was applied to the surface of a plywood sheet of 150mm X4 mm in several applications, and three panels of coating material were applied in parallel for each set of experiments, the thickness of the coating after drying being approximately (0.4. + -. 0.05) mm. According to GB/12441-2018 'finishing type fireproof paint', a large-board combustion method is simulated to carry out a fireproof performance test on an empty wood board and a paint sample: the coating sample plate is placed on a test stand, one surface coated with the fireproof coating faces downwards, the center of the coating sample plate is opposite to a combustor, the temperature of the fire-facing surface rises according to a standard temperature curve, and a thermocouple is arranged on the back surface and connected with a temperature measuring device to record the temperature rise condition of the back surface.
Is coated with nano TiO2The back temperature rise curve of the wood panel with the anti-mildew type transparent fire-retardant coating of Ag is shown in FIG. 1. It can be seen that the temperature of the back surface of the hollow wood board (uncoated) rises quickly when meeting flame, and reaches 220 ℃ in 165s, so that the fire hazard is great; is coated with nano TiO2After the wood board of the anti-mildew type transparent fireproof-coating of Ag is heated, the fire-resistant time is obviously prolonged, the back surface temperature and the temperature rise rate are obviously reduced, and a compact expanded carbon layer (as shown in figure 2) is formed on the surface of the wood board, so that the wood board has better fireproof and heat-insulating properties and further prevents heat transfer.
Containing nano TiO2The results of the simulated large panel combustion method test of the Ag-based mildew-resistant transparent fire-retardant coating are shown in Table 4. It can be seen that the mpva 6 coating panel had the lowest back temperature and the longest fire resistance time at 900s with an expanded carbon layer height of 5.4 cm.
TABLE 4 Nano-TiO containing2Simulated large-plate combustion method test result of anti-mildew type transparent fireproof coating of-Ag
| Sample (I) | Back temperature/deg.C of 900s | Refractory time/s | Height/cm of carbon layer |
| Hollow wood board | - | 100 | - |
| MPPVA0 | 191.6 | 1420 | 5.3 |
| MPPVA1 | 206.5 | 1070 | 3.3 |
| MPPVA2 | 205.0 | 1080 | 4.0 |
| MPPVA3 | 198.3 | 1190 | 4.5 |
| MPPVA4 | 194.4 | 1120 | 4.3 |
| MPPVA5 | 192.4 | 1310 | 5.7 |
| MPPVA6 | 177.1 | 1550 | 5.4 |
| MPPVA7 | 181.7 | 1520 | 5.0 |
SEM images of the surfaces of the carbon layers formed by thermal expansion of MPPVA0 and MPPVA6 are shown in fig. 3. It can be seen that the MPPV 0 has irregular surface shape of the carbon layer formed by thermal expansion, some bubbles are generated, and the compactness is good; the MPPV 6 has folds on the surface of the carbon layer formed by thermal expansion, has no obvious cracks, is in a honeycomb structure, has better surface compactness than the MPPV 0, can more effectively prevent the release of heat, and shows excellent flame-retardant and fireproof performances.
A cell combustion method: the nano TiO-containing material prepared in example 12The mildew-resistant transparent fireproof coating of Ag-MPPVA 0-MPPVA 7 is 250g/m2Three paint panels were coated in parallel runs of each set on plywood panels of 300mm x 150mm x 4mm size. Referring to GB/12441-.
Containing nano TiO2Chamber combustion method for measuring anti-mildew type transparent fireproof coating of-AgThe test results are shown in Table 5, which shows that the wood board coated with nano TiO compared with the untreated hollow wood board2The board mass loss and the carbonization volume of the anti-mildew type transparent fireproof-Ag coating are obviously reduced, the mass loss is less than 3g, and the carbonization volume is less than 25cm3(ii) a Nano TiO 22The addition of Ag affects the fire-retardant properties of the coating, with minimum mass loss of MPPVA6 and minimum charring volume, mass loss of 0.54g and charring volume of 12.6cm3. The reason is that the addition of a proper amount of nano particles can enable the coating to form a more compact and stable expanded carbon layer in the combustion process, and more effectively prevent the heat transfer and the flame propagation. This is consistent with the simulated panel burn test results.
TABLE 5 Nano-TiO-containing2Chamber combustion test results of anti-mildew transparent fireproof-Ag coating
| Sample (I) | Mass loss per g | Charring volume/cm3 | Expansion factor of |
| Hollow wood board | 11.75 | 64.26 | - |
| MPPVA0 | 0.58 | 14 | 93 |
| MPPVA1 | 0.86 | 18 | 100 |
| MPPVA2 | 1.63 | 24.5 | 86 |
| MPPVA3 | 0.93 | 15.43 | 106 |
| MPPVA4 | 0.82 | 13.5 | 86 |
| MPPVA5 | 0.75 | 13.35 | 80 |
| MPPVA6 | 0.54 | 12.6 | 113 |
| MPPVA7 | 0.51 | 14 | 133 |
(4) Analysis of antibacterial Properties of coatings
With reference to GB/T1741-Example 1 preparation of a NanoTiO-containing Material2And (4) carrying out a film mildew resistance test on the Ag mildew-resistant transparent fireproof coating MPPVA 0-MPPVA 7. The mold growth on the surface of the sample is shown in Table 6, and the mold resistance of the sample is shown in Table 7.
TABLE 6 mould growth on the surface of the panels
Note: LP106 and MP6086 are commercially available coating type mildewcide, and experimental groups G1-G5 are formed by coating a layer of mildewcide on the surface of a wood board, and coating a layer of mildewproof transparent fireproof paint after the mildewcide is dried.
TABLE 7 mould resistance rating of the samples
| Sample plate | M | A | B | C | D | E1 | E2 | E3 |
| Mould resistance grade/grade | 4 | 4 | 2 | 4 | 4 | 1 | 1 | 1 |
| Sample plate | E4 | E5 | E6 | E7 | G1 | G2 | G4 | G5 |
| Mould resistance grade/ |
0 | 0 | 0 | 1 | 1 | 1 | 1 | 0 |
As can be seen from tables 6 and 7, a layer containing nano TiO was coated in comparison with the untreated hollow wood board2The mildew-resistant transparent fireproof-coating of-Ag can improve the mildew-resistant grade, because the fireproof-coating has the protection effect on the wood board, prevents mildew spores from directly contacting the wood board, isolates moisture, and reducesThe propagation speed of the mould spores is increased; the mould resistance grades of the experimental groups E1, E2 and E3 are 1 grade, the mould resistance grades of the experimental groups E4, E5 and E6 are 0 grade, and the antibacterial effect is better than that of the control group B, which indicates that the nano TiO is added2The mildew resistance of the Ag-Ag coating is obviously better than that of the coating without nano TiO2-a coating of Ag. Two commercially available mildewcides are selected to carry out control experiments, and the fact that the mildewcide is coated independently is found to be better than the mildewcide containing nano TiO2The mildew-resistant transparent fireproof paint of Ag has weak mildew-resistant effect on wood; the mould resistance grades of the experimental groups G1 and G2 are 1 grade, and the mould resistance grades of the experimental groups G4 and G5 are 1 grade and 0 grade respectively, and are better than the antibacterial effects of the control groups C and D; the comparison of experimental groups G4 and G5 revealed that the coating with the nano TiO under the same mildew preventive was carried out2The growth speed of mould on the surface of the wood board of the-Ag coating MPPVA6 is obviously reduced, which indicates that the wood board contains nano TiO2The coating of-Ag has certain mildew-proof effect.
The results of the antibacterial experiments show that the nano TiO2Ag plays an anti-mould role in the coating, when nano TiO2When the addition amount of-Ag is 1.2%, the anti-mildew effect of the coating is optimal.
(5) Analysis of nanoparticle dispersibility
The transparency of the coating is related to the dispersibility of the nanoparticles in the coating, and the uniform dispersion of the nanoparticles can reduce the scattering of light, thereby reducing the effect on the transparency of the coating. The same part of the MPPV A6 coating is scanned under different magnifications (20000 times and 50000 times), and the distribution of Ag element and Ti element is fluorescently marked.
EDS-mapping images of nano Ag and nano Ti are shown in FIG. 4, when the magnification of an electron microscope is 20000, the nano Ag and the nano Ti are uniformly dispersed in the coating, and when the magnification is increased to 50000, the two nano particles are still uniformly distributed in the coating and do not have an agglomeration phenomenon. Therefore, the nano TiO can be analyzed2The dispersion effect of Ag in the coating is better.
Example 3 Nano SiO containing2Preparation of anti-mildew transparent fireproof coating of-Al-Ag
In proportionMixing nano SiO2Adding Al-Ag into the polyvinyl alcohol phosphate aqueous solution, uniformly stirring at room temperature, then adding aluminum dihydrogen phosphate aqueous solution according to a proportion, and uniformly stirring at room temperature to obtain a component A; taking a methylated melamine formaldehyde resin aqueous solution as a component B; mixing component A and component B at room temperature, standing in shade for 30-60min until no bubbles are formed to obtain the final product containing nanometer SiO2An anti-mold transparent fire-retardant coating of Al-Ag, the solute formulation of which is shown in Table 8.
TABLE 8 contains nano SiO2Solute formula (mass fraction) of anti-mildew transparent fireproof coating of-Al-Ag
| Sample (I) | Methylated melamine formaldehyde resin | Aluminium dihydrogen phosphate | Nano SiO2-Al-Ag | Polyvinyl alcohol phosphoric acid ester |
| MPPVA0 | 6％ | 60％ | 0 | 34％ |
| MPPVA1 | 6％ | 59.8％ | 0.2％ | 34％ |
| MPPVA2 | 6％ | 59.7％ | 0.3％ | 34％ |
| MPPVA3 | 6％ | 59.6％ | 0.4％ | 34％ |
| MPPVA4 | 6％ | 59.5％ | 0.5％ | 34％ |
| MPPVA5 | 6％ | 59.4％ | 0.6％ | 34％ |
Example 4 containing Nano SiO2Characterization of the Properties of the antimycotic transparent fireproof coating of Al-Ag
(1) Coating clarity analysis
The nano SiO-containing material prepared in example 32The mildew-resistant transparent fireproof coating of-Al-Ag is MPPVA 0-MPPVA 5 according to 500g/m2The coated glass sheets were respectively coated on transparent glass sheets of 50mm × 50mm × 3mm, and the transparency of the coating was measured using a light transmittance tester.
The results are shown in Table 9, without the addition of nano SiO2The coating transparency of the transparent fireproof coating MPPVA0 of Al-Ag is the highest; with nano SiO2Increase in amount of-Al-Ag addedThe transparency of the coating is gradually reduced when the nano SiO is used2When the addition amount of-Al-Ag is 0.6%, the transparency of the coating is 86.97% at the lowest, mainly because of the light scattering phenomenon caused by the larger difference between the refractive index of the nano particles and the base resin. Nano SiO 22The addition of Al-Ag reduces the transparency of the coating, but will contain nano SiO2the-Al-Ag mildew-resistant transparent fireproof coating MPPVA 0-MPPVA 5 is respectively coated on the surface of the plywood, the texture structure of the wood can still be clearly seen, the decorative performance of the wood is not influenced, and the condition shows that the wood contains nano SiO2The mildew-resistant transparent fireproof paint of-Al-Ag still has good light transmission performance.
TABLE 9 contains nano SiO2Coating transparency of anti-mildew type transparent fireproof coating of-Al-Ag
| Sample (I) | MPPVA0 | MPPVA1 | MPPVA2 | MPPVA3 | MPPVA4 | MPPVA5 |
| Degree of transparency/%) | 93.12 | 92.56 | 91.78 | 91.26 | 88.69 | 86.97 |
(2) Coating adhesion analysis
The nano SiO-containing coating obtained in example 3 was tested by using a QFH-HD600 adhesion tester, in accordance with GB/T9286-1998 test for marking paint films2-coating adhesion rating of the anti-mildew transparent fire-retardant coating of Al-Ag.
The results are shown in Table 10, the adhesive force grades of the coatings have no obvious difference and are all grade 2, and the requirements on the physical and chemical property adhesive force in the national standard of the finishing type fireproof coating are met.
TABLE 10 contains nano SiO2Coating adhesion grade of anti-mildew type transparent fireproof coating of-Al-Ag
| Sample (I) | MPPVA0 | MPPVA1 | MPPVA2 | MPPVA3 | MPPVA4 | MPPVA5 |
| Adhesion/grade | 2 | 2 | 2 | 2 | 2 | 2 |
(3) Analysis of fire Performance of coatings
Simulating a large-plate combustion method: the nano SiO-containing material prepared in example 32The mildew-resistant transparent fireproof coating of-Al-Ag is MPPVA 0-MPPVA 5 according to 500g/m2The coating was applied to the surface of a plywood sheet of 150mm X4 mm in several applications, and three panels of coating material were applied in parallel for each set of experiments, the thickness of the coating after drying being approximately (0.4. + -. 0.05) mm. According to GB/12441-2018 'finishing type fireproof paint', a large-board combustion method is simulated to carry out a fireproof performance test on an empty wood board and a paint sample: the coating sample plate is placed on a test stand, one surface coated with the fireproof coating faces downwards, the center of the coating sample plate is opposite to a combustor, the temperature of the fire-facing surface rises according to a standard temperature curve, and a thermocouple is arranged on the back surface and connected with a temperature measuring device to record the temperature rise condition of the back surface.
Is coated with SiO containing nano-particles2The back temperature rise curve of the wood panel with the mildew-resistant transparent fireproof coating of-Al-Ag is shown in FIG. 5. It can be seen that the temperature of the back surface of the hollow wood board (uncoated) rises quickly when meeting flame, and reaches 220 ℃ in 165s, so that the fire hazard is great; and is coated with nano SiO-containing2After the wood board of the anti-mildew type transparent fireproof coating of-Al-Ag is heated, the fire-resistant time is obviously prolonged, the back surface temperature and the temperature rise rate are obviously reduced, and a compact expanded carbon layer (shown in figure 6) is formed on the surface of the wood board, so that the wood board has excellent fireproof and heat-insulating properties, further prevents heat transfer and reduces the flame spread rate.
Containing nano SiO2The results of the simulated large panel burning test of the anti-mold type transparent fire-retardant coating material of-Al-Ag are shown in Table 11. It can be seen that the mpva 4 coating panel had the lowest back temperature, the longest fire resistance time, and the highest height of the expanded carbon layer at 900 s.
TABLE 11 contains nano SiO2Simulated large-plate combustion test result of anti-mildew type transparent fireproof coating of-Al-Ag
| Sample (I) | Back temperature of 900 s/deg.C | Refractory time/s | Height/cm of carbon layer |
| MPPVA0 | 191.6 | 1420 | 5.3 |
| MPPVA1 | 186.3 | 1180 | 4.2 |
| MPPVA2 | 196.7 | 1320 | 4.5 |
| MPPVA3 | 173.2 | 1480 | 5.3 |
| MPPVA4 | 136.6 | 1620 | 7.2 |
| MPPVA5 | 173.8 | 1570 | 5.1 |
SEM images of the surfaces of the carbon layers formed by thermal expansion of MPPVA0 and MPPVA4 are shown in fig. 7. It can be seen that the shape of the surface of the carbon layer formed by thermal expansion of the mpva 0 is irregular, and some bubble-like structures exist, which indicates that the formed state of the carbon layer is not stable enough; the MPPVA4 is formed by thermal expansion, the surface of the carbon layer is very dense and continuous, almost has no cracking phenomenon, and is in a regular honeycomb shape. The closed and compact carbon layer can better prevent the transfer of gas and heat and reduce the pyrolysis rate of the surface of the wood board. Thus, containing nano SiO2The carbon layer formed by the Al-Ag coating is more continuous and compact, and has better flame-retardant and fireproof performance.
A cell combustion method: the nano SiO-containing material prepared in example 32The mildew-resistant transparent fireproof coating of-Al-Ag is MPPVA 0-MPPVA 5 according to the weight of 250g/m2Three paint panels were coated in parallel runs of each set on plywood panels of 300mm x 150mm x 4mm size. Referring to GB/12441-.
Containing nano SiO2The results of the Chamber Combustion test of the anti-mold type transparent fire-retardant coating material of-Al-Ag are shown in Table 12, in which the wood board coated with the coating material containing nano SiO was compared with the untreated hollow wood board2The board mass loss and the carbonization volume of the anti-mildew type transparent fireproof coating of-Al-Ag are obviously reduced, the mass loss is less than 3g, and the carbonization volume is less than 25cm3(ii) a And with nano SiO2The fire resistance of the coating shows a tendency of decreasing after increasing due to the increase of the addition amount of Al-Ag, wherein the mass loss and the carbonization volume of the MPPVA4 are minimum, the mass loss is 0.66g, and the carbonization volume is 12.15cm3. The addition of a proper amount of nano particles can enable the coating to form a more compact and stable expanded carbon layer in the combustion process, and more effectively prevent the heat transfer and the flame propagation. This is in contrast to simulationThe test results of the large-plate combustion method are consistent. The result can be obtained by adding proper amount of nano SiO2the-Al-Ag can effectively improve the fireproof performance of the transparent fireproof coating, but the fireproof performance of the coating can be reduced by adding too much or too little Al-Ag, the expansion of a carbon layer is inhibited, and the synergistic flame-retardant effect of the nano particles is reduced.
TABLE 12 contains nano SiO2Chamber combustion test results of an Al-Ag antifungal type transparent fireproof coating
| Sample (I) | Mass loss per g | Charring volume/cm3 | Expansion factor |
| Hollow wood board | 11.75 | 64.26 | - |
| MPPVA0 | 0.58 | 14 | 93 |
| MPPVA1 | 0.85 | 22.5 | 53 |
| MPPVA2 | 1.19 | 18 | 62 |
| MPPVA3 | 0.73 | 15.3 | 100 |
| MPPVA4 | 0.66 | 12.15 | 120 |
| MPPVA5 | 0.97 | 12.25 | 93 |
(4) Analysis of antibacterial Properties of coatings
The nano SiO-containing material prepared in example 3 is determined by reference to GB/T1741-2020 paint film mildew resistance determination method2And (4) carrying out a mould resistance test on the paint film by using Al-Ag mould-resistant transparent fireproof paint MPPVA 0-MPPVA 5. The mold growth on the surface of the sample is shown in Table 13, and the mold resistance of the sample is shown in Table 14.
TABLE 13 mould growth on the surface of the panels
Note: LP106 and MP6086 are commercially available coating type mildewcide, and experimental groups G1-G6 are formed by coating a layer of mildewcide on the surface of a wood board, and coating a layer of fireproof paint after the mildewcide is dried.
TABLE 14 sample resistance to mold
| Sample plate | M | A | B | C | D | F1 | F2 | F3 |
| Mould resistance grade/grade | 4 | 4 | 2 | 4 | 4 | 0 | 0 | 0 |
| Sample plate | F4 | F5 | G1 | G3 | G4 | G6 | ||
| Mould resistance grade/ |
0 | 0 | 1 | 0 | 1 | 0 |
As can be seen from tables 13 and 14, compared with the control group a, the growth rate of mold on the surface of the control group B is significantly slowed, no mold grows on the surface of the wood board within 21 days, and mold grows moderately on the back of the wood board at 28 days, because the wood board is protected by the fireproof coating, the contact with moisture and oxygen is reduced, and the mold cannot directly absorb the nutrient substances in the wood fiber, so the propagation rate is slowed; within 28 days, the surfaces of the wood boards of the experimental groups F1-F5 are not corroded by mould, no mould grows, the mould resistance grades are all 0 grade, the antibacterial effect is better than that of the control group B, and the addition of the nano SiO is proved2The mildew-proof and antibacterial performance of the-Al-Ag coating is obviously better than that of the coating without the addition of nano SiO2-coating of Al-Ag. Two commercially available mildew inhibitors are selected for carrying out a control experiment, and the fact that the antibacterial performance of the wood board cannot be enhanced by independently coating the two mildew inhibitors on the surface of the wood board is found, because the mildew can directly contact the surface of the wood board under the appropriate temperature and humidity condition without the protection of a coating, nutrient substances in the wood board are absorbed, and the growth of the mildew inhibitors is facilitated; at day 28, the coverage rate of the mildew on the surfaces of the wood boards of the experimental groups G1 and G4 is less than 30%, the mildew resistance grade is 1 grade, and compared with the control group B, the mildew resistance grade is improved, because the antibacterial agent and the coating play a role in inhibiting the growth of the mildew, the growth speed of the mildew is delayed; experimental groups G3 and G6 plank Table within 28 daysThe growth of mould is not seen, the mould resistance grade reaches 0 grade, and compared with experimental groups G1 and G4, the mould resistance grade is improved by one grade, which shows that the nano SiO-containing material of the invention2the-Al-Ag coating MPPVA4 also plays an antibacterial role at the same time, and the antibacterial effect is obvious.
The results of the antibacterial experiments show that the nano SiO2the-Al-Ag has excellent antibacterial performance in the transparent fireproof coating, can inhibit the growth of mould and prolong the service life of the wood board substrate. When nano SiO2When the addition amount of-Al-Ag is 0.5%, the antibacterial effect of the coating is optimal.
(5) Analysis of nanoparticle dispersibility
The transparency of the coating is related to the dispersibility of the nanoparticles in the coating, and the uniform dispersion of the nanoparticles can reduce the scattering of light, thereby reducing the effect on the transparency of the coating. The same part of the MPPV A4 coating is scanned under different magnifications (20000 times and 50000 times), and the distribution of Ag element and Si element is fluorescently marked.
EDS-mapping images of nano Ag and nano Si are shown in FIG. 8, when the magnification of an electron microscope is 20000, the nano Ag and the nano Si are uniformly dispersed in the coating, and when the magnification is increased to 50000, the two nano particles are still uniformly distributed in the coating and do not have the agglomeration phenomenon. Therefore, nano SiO can be analyzed2The dispersion effect of the-Al-Ag in the coating is better.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (2)
1. The mildew-resistant transparent fireproof coating is characterized in that: the solute comprises the following components in percentage by mass: 6 percent of methylated melamine formaldehyde resin, 34 percent of polyvinyl alcohol phosphate, 1.2 percent of nano titanium dioxide silver-loaded or 0.5 percent of nano silicon dioxide aluminum silver-loaded, and the balance of aluminum dihydrogen phosphate.
2. The method for preparing the anti-mold type transparent fireproof coating of claim 1, wherein: the method comprises the following steps: adding the silver-loaded nano titanium dioxide or the silver-loaded nano silicon aluminum oxide into the aqueous solution of polyvinyl alcohol phosphate according to the proportion, uniformly stirring, then adding the aqueous solution of aluminum dihydrogen phosphate according to the proportion, and uniformly stirring to obtain a component A; taking a methylated melamine formaldehyde resin aqueous solution as a component B; and uniformly stirring the component A and the component B in proportion, and standing until no bubbles exist to obtain the mildew-resistant transparent fireproof coating.
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