CN112981401B - Stainless steel plate for cabinet - Google Patents
Stainless steel plate for cabinet Download PDFInfo
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- CN112981401B CN112981401B CN202110156557.4A CN202110156557A CN112981401B CN 112981401 B CN112981401 B CN 112981401B CN 202110156557 A CN202110156557 A CN 202110156557A CN 112981401 B CN112981401 B CN 112981401B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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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
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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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
- 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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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/362—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also zinc cations
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
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Abstract
The application discloses stainless steel sheet material for cupboard includes base plate layer and antibiotic layer, the base plate layer is stainless steel's board-type spare, antibiotic layer cladding is in the surface of base plate layer, antibiotic layer is made by following parts by weight material: 35-40 parts of fluorocarbon resin, 3-5 parts of acrylic resin, 10-15 parts of dimethylbenzene, 3-5 parts of cyclohexanone, 2-3 parts of ethyl acetate, 6-8 parts of HDI curing agent and 2-3 parts of nano antibacterial particles; the nano antibacterial particles comprise SiO with a core-shell structure2/TiO2And (3) granules. According to the method, the antibacterial coating is coated on the surface of the stainless steel substrate, as the pore diameters of silicon dioxide in the antibacterial particles adopted in the antibacterial coating are uniform, and the inner surface of a pore channel is enriched with electrons, the photocatalytic performance and the antibacterial performance of the antibacterial coating are effectively improved, and meanwhile, the nano particles prepared by the method can be uniformly and effectively dispersed on the surface of the stainless steel substrate, so that the prepared stainless steel plate has excellent antibacterial lasting performance.
Description
Technical Field
The application relates to the field of stainless steel materials, in particular to a stainless steel plate for a cabinet.
Background
The stainless steel has high strength, good corrosion resistance and formability, and various varieties, is suitable for the requirements of various products, and is widely applied to various products in different fields. Stainless steel has been widely used in kitchen utensils and appliances, transportation, bathroom sanitary wares, domestic appliance, architectural decoration and medical instrument etc. each field, and stainless steel material also has good performance in the kitchen, so adopt stainless steel material as the material of kitchen cupboard to prepare, can effectively embody good performance.
Although the stainless steel material has obvious function of inhibiting microorganisms in the using process, the use requirement, particularly the antibacterial performance, of the existing stainless steel material as a cabinet cannot be effectively met, the existing cabinet material stainless steel has poor sterilization effect and has non-lasting antibacterial performance, and the defects greatly reduce the antibacterial performance and the durability of the antibacterial stainless steel in practical application.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art.
In view of the above, the present invention provides a stainless steel sheet for a cabinet, which has excellent and durable antibacterial properties and can be widely used as a cabinet sheet.
The stainless steel plate for the cabinet comprises a substrate layer and an antibacterial layer, wherein the substrate layer is a plate-shaped piece made of a stainless steel material, the antibacterial layer is coated on the surface of the substrate layer, and the antibacterial layer is prepared from the following substances in parts by weight: 35-40 parts of fluorocarbon resin, 3-5 parts of acrylic resin, 10-15 parts of dimethylbenzene, 3-5 parts of cyclohexanone, 2-3 parts of ethyl acetate, 6-8 parts of HDI curing agent and 2-3 parts of nano antibacterial particles; the nano antibacterial particles comprise SiO with a core-shell structure2/TiO2And (3) granules.
According to the stainless steel plate for the cabinet, disclosed by the embodiment of the invention, the surface of the stainless steel substrate is coated with the antibacterial coating, and the antibacterial particles (SiO with a core-shell structure) are added into the antibacterial coating2/TiO2Particles), because the aperture of the silicon dioxide in the antibacterial particles is uniform, the antibacterial particles have high specific surface area and large adsorption capacity, the inner surface of the pore channel has electron enrichment to generate a strong magnetic field, the electron-hole recombination can be inhibited, and the photoresponse range of the titanium dioxide is increased, so that the photocatalytic performance and the antibacterial performance of the titanium dioxide are effectively improved.
The stainless steel plate for the cabinet according to the embodiment of the invention can also have the following additional technical characteristics:
according to one embodiment of the present invention, the nano antibacterial particles are prepared by the following scheme: (1) preparing matrix microsphere particles: respectively weighing 80-100 parts by weight of ammonia water, 10-15 parts by weight of polyacrylic acid and 20-30 parts by weight of ethyl orthosilicate, stirring and mixing, collecting a mixed solution, adding the mixed solution into absolute ethyl alcohol according to a mass ratio of 1: 6-8, stirring at room temperature, performing centrifugal separation, taking a lower layer precipitate, and drying to obtain matrix microsphere particles; (2) coating and preparing a shell: respectively weighing 4-5 parts of matrix microsphere particles, 1-2 parts of graphene, 100-200 parts of deionized water, 15-20 parts of absolute ethyl alcohol and 1-2 parts of tetrabutyl titanate according to parts by weight, stirring, mixing, ultrasonically dispersing, carrying out heat preservation and reflux treatment, standing and cooling to room temperature, filtering, collecting lower-layer precipitates, carrying out heat preservation and calcination treatment, standing and cooling to room temperature, and grinding to obtain the nano composite nanoparticles.
According to an embodiment of the invention, the heat-preservation calcining treatment is heat-preservation calcining at 750-800 ℃ for 2-3 h.
According to one embodiment of the present invention, a connection layer is further disposed between the substrate layer and the antibacterial layer, and the connection layer is composed of the following substances in parts by weight: 40-60 parts of zinc dihydrogen phosphate, 20-30 parts of zinc nitrate, 1-2 parts of sodium chlorate, 1-2 parts of tartaric acid, 1-2 parts of emulsifier and 300-500 parts of water.
According to an embodiment of the present invention, the connection layer further includes 6 to 8 parts by weight of a coupling agent.
According to one embodiment of the invention, the coupling agent is any one or more of a silane coupling agent KH-550, a silane coupling agent KH-560 and a silane coupling agent KH-570.
The stainless steel plate for the cabinet according to one embodiment of the invention is prepared by the following preparation method: s1, base layer treatment: taking a stainless steel plate-shaped member, degreasing and degreasing the surface of the stainless steel plate-shaped member, naturally drying the stainless steel plate-shaped member, and then polishing and roughening the surfaces of two sides of the stainless steel plate-shaped member to obtain a modified substrate layer; s2, coating of a connecting layer: mixing zinc dihydrogen phosphate, zinc nitrate, sodium chlorate, tartaric acid, an emulsifier, water and a silane coupling agent according to a formula to prepare a connection modification liquid, placing a modified substrate layer into the connection modification liquid, standing at room temperature for 6-8 min, washing and drying to obtain a connection layer coated substrate; s3, coating of an antibacterial layer: stirring and mixing fluorocarbon resin, acrylic resin, dimethylbenzene, cyclohexanone, ethyl acetate, an HDI curing agent and nano antibacterial particles according to a formula, placing the mixture in a spray coating device, performing spray coating treatment at room temperature until the connecting layer coats two sides of the substrate, and curing at room temperature to finish the preparation of the stainless steel plate for the cabinet.
According to an embodiment of the present invention, the surface roughness of the modified base layer after the roughening treatment described in step S1 is ra0.1.
According to one embodiment of the invention, the thickness of the connecting layer is 0.2-0.3 μm, and the thickness of the antibacterial layer is 0.3-0.5 μm.
According to an embodiment of the invention, the pressure of the spraying process in the step S3 is 0.3-0.5 MPa.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
Reference will now be made in detail to the embodiments of the present invention, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The following examples are illustrative only and are not to be construed as limiting the invention.
Hereinafter, a stainless steel sheet for a cabinet and a method for manufacturing the same according to an embodiment of the present invention will be described in detail.
Firstly, the stainless steel plate for the cabinet according to the embodiment of the invention comprises a substrate layer and an antibacterial layer, wherein the substrate layer is a plate-shaped member made of stainless steel, the antibacterial layer is coated on the surface of the substrate layer, and the antibacterial layer is made of the following materials in parts by weight: 35-40 parts of fluorocarbon resin, 3-5 parts of acrylic resin, 10-15 parts of dimethylbenzene, 3-5 parts of cyclohexanone, 2-3 parts of ethyl acetate, 6-8 parts of HDI curing agent and 2-3 parts of nano antibacterial particles; the nano antibacterial particles comprise SiO with a core-shell structure2/TiO2And (3) granules.
Therefore, according to the stainless steel plate for the cabinet provided by the embodiment of the invention, the surface of the stainless steel substrate is coated with the antibacterial coating, and the antibacterial particles (SiO with the core-shell structure) added in the antibacterial coating2/TiO2Particles), because the aperture of the silicon dioxide in the antibacterial particles is uniform, the silicon dioxide has high specific surface area and large adsorption capacity, the inner surface of the pore channel has electron enrichment, a strong magnetic field is generated, the electron-hole recombination can be inhibited, the photoresponse range of the titanium dioxide is increased, and the photocatalytic performance and the antibacterial performance of the titanium dioxide are effectively improvedThe surface of the stainless steel plate forms a good dispersion system, so that the prepared stainless steel plate has excellent antibacterial durability.
According to one embodiment of the present invention, the nano antibacterial particles are prepared by the following scheme: (1) preparing matrix microsphere particles: respectively weighing 80-100 parts by weight of ammonia water, 10-15 parts by weight of polyacrylic acid and 20-30 parts by weight of ethyl orthosilicate, stirring and mixing, collecting a mixed solution, adding the mixed solution into absolute ethyl alcohol according to a mass ratio of 1: 6-8, stirring at room temperature, performing centrifugal separation, taking a lower layer precipitate, and drying to obtain matrix microsphere particles; (2) coating and preparing a shell: respectively weighing 4-5 parts of matrix microsphere particles, 1-2 parts of graphene, 100-200 parts of deionized water, 15-20 parts of absolute ethyl alcohol and 1-2 parts of tetrabutyl titanate according to parts by weight, stirring, mixing, ultrasonically dispersing, carrying out heat preservation and reflux treatment, standing and cooling to room temperature, filtering, collecting lower-layer precipitates, carrying out heat preservation and calcination treatment, standing and cooling to room temperature, and grinding to obtain the nano composite antibacterial particles.
By adopting the technical scheme, in the scheme for preparing the nano antibacterial particles, the graphene material is added in the scheme for coating the shell, and has excellent size effect and dispersion performance, so that the graphene material is effectively coated on the surface of the microsphere particles of the matrix, and in the subsequent calcining process, the graphene in the shell is pyrolyzed to generate carbon dioxide to volatilize, so that a uniformly dispersed pore structure is formed on the surface of the shell of the nano antibacterial particles, the specific surface area and the adsorption capacity of the composite particle material are further improved, and in the subsequent loading adding process, a good dispersion filling effect is formed, so that the prepared antibacterial particles can be uniformly and effectively dispersed on the surface of the stainless steel matrix to form a good dispersion system, and the prepared stainless steel plate has excellent antibacterial durability.
In some embodiments of the invention, the heat-preservation calcining treatment is heat-preservation calcining at 750-800 ℃ for 2-3 h.
Therefore, according to the technical scheme, in the process of heat preservation and calcination treatment, the temperature of calcination treatment is optimized, the calcination temperature is improved, composite particles can be effectively formed, meanwhile, effective calcination treatment is carried out at the temperature, the graphene materials filled in a dispersing mode can be effectively pyrolyzed, and therefore the prepared antibacterial particles have excellent specific surface area and dispersing performance, and the prepared stainless steel plate has excellent antibacterial durability.
Further, a connecting layer is arranged between the substrate layer and the antibacterial layer, and the connecting layer is composed of the following substances in parts by weight: 40-60 parts of zinc dihydrogen phosphate, 20-30 parts of zinc nitrate, 1-2 parts of sodium chlorate, 1-2 parts of tartaric acid, 1-2 parts of emulsifier and 300-500 parts of water.
Through adopting above-mentioned technical scheme, because this application adopts zinc dihydrogen phosphate to prepare the articulamentum as the main raw materials, on the one hand, the setting of articulamentum, good interface structure has been formed between antibiotic layer and the base member layer, thereby the performance of antibiotic layer cladding has been improved, antibiotic endurance quality in the antibiotic layer in-service use process has been improved, on the other hand, the component of articulamentum has been optimized in this application, make the articulamentum form the even concave-convex structure that links to each other, thereby make antibiotic layer have fine adhesive force and roughness, thereby the antibiotic endurance quality of stainless steel sheet material has effectively been improved.
According to an embodiment of the present invention, the connection layer further includes 6 to 8 parts by weight of a coupling agent.
By adopting the technical scheme, the coupling agent is any one or more of a silane coupling agent KH-550, a silane coupling agent KH-560 and a silane coupling agent KH-570.
By adopting the technical scheme, because the silane coupling agent is used for modification treatment on the surface of the material, and the silane coupling agent material and the metal act to perform dehydration reaction with organic matters, a compact connecting layer is formed on the surface of the metal plate, the stability and compactness of the structure of the connecting layer are further improved, the structural performance of the surface of the stainless steel material is improved, and the antibacterial durability of the stainless steel material is effectively improved.
The stainless steel plate for the cabinet provided by the embodiment of the invention is prepared by the following preparation method: s1, base layer treatment: taking a stainless steel plate-shaped member, degreasing and degreasing the surface of the stainless steel plate-shaped member, naturally drying the stainless steel plate-shaped member, and then polishing and roughening the surfaces of two sides of the stainless steel plate-shaped member to obtain a modified substrate layer; s2, coating of a connecting layer: mixing zinc dihydrogen phosphate, zinc nitrate, sodium chlorate, tartaric acid, an emulsifier, water and a silane coupling agent according to a formula to prepare a connection modification liquid, placing a modified substrate layer into the connection modification liquid, standing at room temperature for 6-8 min, washing and drying to obtain a connection layer coated substrate; s3, coating of an antibacterial layer: stirring and mixing fluorocarbon resin, acrylic resin, dimethylbenzene, cyclohexanone, ethyl acetate, an HDI curing agent and nano antibacterial particles according to a formula, placing the mixture in a spray coating device, performing spray coating treatment at room temperature until the connecting layer coats two sides of the substrate, and curing at room temperature to finish the preparation of the stainless steel plate for the cabinet.
Therefore, the surface structure of the stainless steel material is optimized by the scheme of coating layer by layer, and the antibacterial lasting performance of the surface of the stainless steel material can be effectively improved by the multi-layer coating structure.
According to one embodiment of the invention, the thickness of the connecting layer is 0.2-0.3 μm, and the thickness of the antibacterial layer is 0.3-0.5 μm.
From this, this application has optimized the thickness of articulamentum and the thickness of antibiotic layer, and the articulamentum after optimizing on the one hand and antibiotic layer can prevent that the film thickness is too big, lead to whole cladding structure's cladding performance not good to take place the phenomenon that drops, and in the aspect of another method, also effectively improve cladding structure thickness and hang down excessively, lead to the cladding antibiotic and the not enough excellent defect of connectivity, thereby make the stainless steel panel for cabinet of preparation have good antibiotic endurance quality.
According to an embodiment of the invention, the pressure of the spraying process in the step S3 is 0.3-0.5 MPa.
Therefore, the spraying pressure is optimized, so that the antibacterial layer coated on the surface of the connecting layer is effectively coated on the surface of the connecting layer to form effective coating, the phenomenon that the antibacterial layer is easy to fall off is improved, and the prepared stainless steel plate for the cabinet has good antibacterial durability.
In some embodiments of the present invention, the surface roughness of the modified base layer after the roughening treatment in step S1 is ra0.1.
Therefore, the surface roughness of the modified substrate layer is optimized, the bonding strength between the surface of the substrate layer and the connecting layer is effectively improved, the bonding strength of the subsequent coating of the antibacterial layer is effectively improved, and the prepared stainless steel plate for the cabinet has good antibacterial durability.
In summary, an antibacterial coating is coated on the surface of the stainless steel substrate, and antibacterial particles (SiO with core-shell structure) are added into the antibacterial coating2/TiO2Particles), because the aperture of the silicon dioxide in the antibacterial particles is uniform, the particles have high specific surface area and large adsorption capacity, the inner surface of the pore channel has electron enrichment to generate a strong magnetic field, the electron-hole recombination can be inhibited, and the photoresponse range of the titanium dioxide is increased, so that the photocatalytic performance and the antibacterial performance of the titanium dioxide are effectively improved, and meanwhile, the nano particles prepared by the method can be uniformly and effectively dispersed on the surface of a stainless steel matrix to form a good dispersion system, so that the prepared stainless steel plate has excellent antibacterial lasting performance;
meanwhile, in the scheme for preparing the nano antibacterial particles, the graphene material is added in the scheme for coating the shell, and has excellent size effect and dispersion performance, so that the graphene material is effectively coated on the surface of the matrix microsphere particles, and in the subsequent calcining process, the graphene in the shell is pyrolyzed to generate carbon dioxide to volatilize, so that a uniformly dispersed pore structure is formed on the surface of the shell of the nano antibacterial particles, the specific surface area and the adsorption capacity of the composite particle material are further improved, and in the subsequent loading adding process, a good dispersion filling effect is formed, so that the prepared antibacterial particles can be uniformly and effectively dispersed on the surface of the stainless steel matrix to form a good dispersion system, and the prepared stainless steel plate has excellent antibacterial durability.
The stainless steel plate for cabinets and the preparation method thereof according to the embodiments of the present invention will be described in detail with reference to the following embodiments.
The present application will be described in further detail with reference to examples.
In the examples of the present application, the raw materials and the equipment used are as follows, but not limited thereto:
in the application, all raw materials and instruments and equipment can be obtained by market, and the specific models are as follows:
silane coupling agents KH-550, KH-560 and KH-570;
digital display type heating magnetic stirrer RH ditigan.
Preparation example 1
Adding 100g of polyacrylic acid into 800g of 15% ammonia water by mass fraction, stirring and mixing, adding into 6600g of absolute ethyl alcohol to obtain a mixed solution, adding 200g of tetraethoxysilane into the mixed solution, stirring and mixing, placing at 25 ℃ for heat preservation reaction for 8 hours, carrying out centrifugal separation, collecting lower-layer precipitate, washing and drying to obtain matrix microsphere particles; respectively weighing 400g of substrate microsphere particles, 100g of graphene, 10kg of deionized water, 1500g of absolute ethyl alcohol and 100g of tetrabutyl titanate, placing at 55 ℃, performing ultrasonic dispersion for 15min, performing heat preservation and reflux treatment for 6h, standing and cooling to room temperature, filtering, collecting lower-layer precipitates, performing heat preservation and calcination at 750 ℃ for 2h, standing and cooling to room temperature, and grinding to obtain the nano antibacterial particles 1.
Preparation example 2
Adding 120g of polyacrylic acid into 900g of 15% ammonia water by mass fraction, stirring and mixing, adding into 7700g of absolute ethyl alcohol to obtain a mixed solution, adding 250g of tetraethoxysilane into the mixed solution, stirring and mixing, placing at 27 ℃ for heat preservation reaction for 9 hours, carrying out centrifugal separation, collecting lower-layer precipitate, washing and drying to obtain matrix microsphere particles; respectively weighing 450g of matrix microsphere particles, 100g of graphene, 15kg of deionized water, 1500g of absolute ethyl alcohol and 150g of tetrabutyl titanate, placing the materials at 60 ℃, performing ultrasonic dispersion for 17min, performing heat preservation reflux treatment for 7h, standing and cooling to room temperature, filtering, collecting lower-layer precipitates, performing heat preservation calcination at 775 ℃ for 2h, standing and cooling to room temperature, and grinding to obtain the nano antibacterial particles 2.
Preparation example 3
Adding 150g of polyacrylic acid into 1000g of 15% ammonia water with mass fraction, stirring and mixing, adding 8800g of absolute ethyl alcohol again to obtain a mixed solution, adding 300g of tetraethoxysilane into the mixed solution, stirring and mixing, placing at 30 ℃ for heat preservation reaction for 10 hours, carrying out centrifugal separation, collecting lower-layer precipitate, washing and drying to obtain matrix microsphere particles; respectively weighing 500g of matrix microsphere particles, 200g of graphene, 20kg of deionized water, 2000g of absolute ethyl alcohol and 200g of tetrabutyl titanate, placing the mixture at 65 ℃, performing ultrasonic dispersion for 20min, performing heat preservation reflux treatment for 8h, standing and cooling to room temperature, filtering, collecting lower-layer precipitates, performing heat preservation calcination at 800 ℃ for 3h, standing and cooling to room temperature, and grinding to obtain the nano antibacterial particles 3.
Preparation example 4
400g of zinc dihydrogen phosphate, 200g of zinc nitrate, 10g of sodium chlorate, 10g of tartaric acid, 60g of silane coupling agent, 10g of emulsifier and 3000g of water are respectively taken, stirred and mixed to obtain the connection modified liquid 1.
Preparation example 5
500g of zinc dihydrogen phosphate, 250g of zinc nitrate, 15g of sodium chlorate, 15g of tartaric acid, 70g of silane coupling agent, 15g of emulsifier and 4000g of water are respectively taken, stirred and mixed to obtain a connection modified liquid 2.
Preparation example 6
600g of zinc dihydrogen phosphate, 300g of zinc nitrate, 20g of sodium chlorate, 20g of tartaric acid, 80g of silane coupling agent, 20g of emulsifier and 5000g of water are respectively taken, stirred and mixed to obtain a connection modified liquid 3.
Example 1
Treating a substrate layer: taking a stainless steel plate-shaped member, degreasing and degreasing the surface of the stainless steel plate-shaped member, naturally drying the stainless steel plate-shaped member, and then polishing and roughening the surfaces of two sides of the stainless steel plate-shaped member until the surface roughness is Ra0.1 to obtain a modified substrate layer;
coating a connecting layer: placing the modified substrate layer in the connection modification liquid 1, standing at room temperature for 6-8 min, washing and drying to obtain a connection layer coated substrate with the connection layer thickness of 0.2 mu m;
coating an antibacterial layer: and (2) mixing 350g of fluorocarbon resin, 30g of acrylic resin, 100g of dimethylbenzene, 30g of cyclohexanone, 20g of ethyl acetate, 60g of HDI curing agent and 20g of nano antibacterial particles 1, stirring, placing in a spray coating device, performing spray coating treatment at room temperature, controlling the spray coating pressure to be 0.3MPa, spraying to two sides of a connecting layer coated substrate, controlling the thickness of an antibacterial layer to be 0.3 mu m, and curing at room temperature to complete the preparation of the stainless steel plate for the cabinet.
Examples 2 to 7
Examples 2 to 7: the stainless steel plate for cabinets is different from example 1 in that the raw material ratio and preparation parameters are shown in table 1, and the rest of the preparation steps and the preparation environment are the same as those of example 1.
Table 1 table of the ingredient ratios of the raw materials of examples 1 to 9
Example 8
The stainless steel plate for cabinets is different from example 1 in that the spraying pressure is 0.5MPa in the preparation process of the antibacterial coating in example 8.
Example 9
The stainless steel plate for cabinets is different from example 1 in that the thickness of the antibacterial layer is 0.5 μm in the preparation process of the antibacterial layer coating in example 8.
Comparative example
Comparative example 1
Stainless steel cabinet panels are different from those of example 1 in that nano-titanium dioxide is directly used in comparative example 1 instead of the nano-antibacterial particles 1 prepared in example 1 of the present application.
Comparative example 2
Stainless steel cabinet panels are different from those of example 1 in that nano-silica is directly used in comparative example 2 instead of the nano-antibacterial particles 1 prepared in example 1 of the present application.
Comparative example 3
Stainless steel cabinet panels are different from example 1 in that a mixture of nano titanium dioxide and nano silicon dioxide mixed by equal mass is used in comparative example 3 instead of the nano antibacterial particles 1 prepared in example 1.
Comparative example 4
Stainless steel cabinet sheets are different from example 1 in that no tie layer is added between the antibacterial layer and the substrate layer in comparative example 4.
Performance test
The stainless steel plates for cabinets prepared in examples 1 to 9 and comparative examples 1 to 4 were subjected to the antibacterial property test, respectively.
Detection method/test method
Cutting the prepared plate into a sample of 40mm multiplied by 40mm, wherein the experimental microorganism adopts escherichia coli and staphylococcus aureus, and the experimental procedure is as follows:
(1) autoclaving the ethanol-washed sample and the control stainless steel sample at 121 deg.C for 20 min;
(2) diluting the inoculated strain with PBS solution to 10%5cfu/mL of standard bacterial liquid, and respectively and uniformly dripping 0.5mL of bacterial liquid on the surface of the stainless steel sample boiled by water for 5 hours, and covering with a sterile plastic film.
(3) And putting the sample coated with the bacterial liquid on the surface and the contrast stainless steel sample into an incubator with the temperature of 35 ℃ and the humidity of 90% for 24 hours of bacterial culture.
(4) The plates were placed in an incubator at 35 ℃ for 48 hours by the plate method (agar culture method) and finally the number of bacteria was counted from the plastic plate and the sterilization rate was calculated.
The specific detection results are shown in the following table 2:
referring to the comparison of the performance tests of table 2, it can be found that:
(1) the stainless steel plates prepared in embodiments 1 to 9 have good antibacterial durability, that is, after being boiled in water for 5 hours, the antibacterial property of the stainless steel plates reaches more than 98%, which indicates that the technical scheme of the application coats an antibacterial coating on the surface of a stainless steel substrate, and antibacterial particles (SiO with a core-shell structure) are added into the antibacterial coating2/TiO2Particles) because the silicon dioxide in the antibacterial particles has uniform aperture, high specific surface area and large adsorption capacity, the inner surface of the pore channel has electron enrichment to generate a strong magnetic field and can inhibit electricityThe compound of the sub-cavity and the cavity increases the photoresponse range of the titanium dioxide, thereby effectively improving the photocatalytic performance and the antibacterial performance of the titanium dioxide, and meanwhile, the nano-particles prepared by the method can be uniformly and effectively dispersed on the surface of a stainless steel matrix to form a good dispersion system, so that the prepared stainless steel plate has excellent antibacterial lasting performance.
(2) Comparing the technical scheme of the application with comparative examples 1 to 3, and because the compositions and preparation methods of the antibacterial particles are adjusted in the comparative examples 1 to 3, the antibacterial performance of the antibacterial particles is obviously reduced, which shows that in the scheme of preparing the nano antibacterial particles, the graphene material is added in the scheme of coating the shell, and because the graphene material has excellent size effect and dispersion performance, the graphene material is effectively coated on the surface of the substrate microsphere particles, in the subsequent calcining process, carbon dioxide is generated after the graphene in the shell is pyrolyzed and is volatilized, so that a uniformly dispersed pore structure is formed on the surface of the shell of the nano antibacterial particles, the specific surface area and the adsorption capacity of the composite particle material are further improved, in the subsequent loading process, a good dispersed filling effect is formed, and the prepared antibacterial particles can be uniformly and effectively dispersed on the surface of a stainless steel substrate to form a good dispersion system, thereby the prepared stainless steel plate has excellent antibacterial durability.
(4) Comparing embodiment 1 and comparative example 4 of the technical scheme of the application, the antibacterial property of comparative example 4 is obviously reduced, which shows that the technical scheme of the application adopts zinc dihydrogen phosphate as the main raw material to prepare the connecting layer, on one hand, the setting of the connecting layer forms a good interface structure between the antibacterial layer and the substrate layer, thereby improving the performance of the antibacterial layer coating, and improving the antibacterial lasting performance of the antibacterial layer in the actual use process, on the other hand, the components of the connecting layer are optimized, so that the connecting layer forms a uniformly connected concave-convex structure, thereby the antibacterial layer has good adhesive force and flatness, and the antibacterial lasting performance of the stainless steel plate is effectively improved.
While embodiments of the invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Claims (7)
1. The stainless steel plate for the cabinet is characterized by comprising a substrate layer and an antibacterial layer, wherein the substrate layer is a plate-shaped member made of stainless steel, the antibacterial layer is coated on the surface of the substrate layer, and the antibacterial layer is prepared from the following substances in parts by weight:
35-40 parts of fluorocarbon resin;
3-5 parts of acrylic resin;
10-15 parts of dimethylbenzene;
3-5 parts of cyclohexanone;
2-3 parts of ethyl acetate;
6-8 parts of an HDI curing agent;
2-3 parts of nano antibacterial particles;
the nano antibacterial particles comprise SiO with a core-shell structure2/TiO2Particles;
a connecting layer is also arranged between the substrate layer and the antibacterial layer, and the connecting layer is prepared from a connecting modification liquid consisting of the following substances in parts by weight:
40-60 parts of zinc dihydrogen phosphate;
20-30 parts of zinc nitrate;
1-2 parts of sodium chlorate;
1-2 parts of tartaric acid;
1-2 parts of an emulsifier;
6-8 parts of a coupling agent;
300-500 parts of water;
the nano antibacterial particles are prepared by adopting the following scheme:
(1) preparing matrix microsphere particles: respectively weighing 80-100 parts by weight of ammonia water, 10-15 parts by weight of polyacrylic acid and 20-30 parts by weight of ethyl orthosilicate, stirring and mixing, collecting a mixed solution, adding the mixed solution into absolute ethyl alcohol according to a mass ratio of 1: 6-8, stirring at room temperature, performing centrifugal separation, taking a lower layer precipitate, and drying to obtain matrix microsphere particles;
(2) coating and preparing a shell: respectively weighing 4-5 parts of matrix microsphere particles, 1-2 parts of graphene, 100-200 parts of deionized water, 15-20 parts of absolute ethyl alcohol and 1-2 parts of tetrabutyl titanate according to parts by weight, stirring, mixing, ultrasonically dispersing, carrying out heat preservation and reflux treatment, standing and cooling to room temperature, filtering, collecting lower-layer precipitates, carrying out heat preservation and calcination treatment, standing and cooling to room temperature, and grinding to prepare the composite nanoparticles.
2. The stainless steel plate for the cupboard as claimed in claim 1, wherein the heat-preservation calcination treatment is heat-preservation calcination at 750-800 ℃ for 2-3 h.
3. The stainless steel plate for cabinets of claim 1, wherein the coupling agent is any one or more of a silane coupling agent KH-550, a silane coupling agent KH-560 and a silane coupling agent KH-570.
4. The stainless steel plate for cabinets of any one of claims 1 to 3, wherein the stainless steel plate for cabinets is prepared by the following preparation method:
s1, base layer treatment: taking a stainless steel plate-shaped member, degreasing and degreasing the surface of the stainless steel plate-shaped member, naturally drying the stainless steel plate-shaped member, and then polishing and roughening the surfaces of two sides of the stainless steel plate-shaped member to obtain a modified substrate layer;
s2, coating of a connecting layer: mixing zinc dihydrogen phosphate, zinc nitrate, sodium chlorate, tartaric acid, an emulsifier, water and a silane coupling agent according to a formula to prepare a connection modification liquid, placing a modified substrate layer into the connection modification liquid, standing at room temperature for 6-8 min, washing and drying to obtain a connection layer coated substrate;
s3, coating of an antibacterial layer: stirring and mixing fluorocarbon resin, acrylic resin, dimethylbenzene, cyclohexanone, ethyl acetate, an HDI curing agent and nano antibacterial particles according to a formula, placing the mixture in a spray coating device, performing spray coating treatment at room temperature until the connecting layer coats two sides of the substrate, and curing at room temperature to finish the preparation of the stainless steel plate for the cabinet.
5. The stainless steel cabinet sheet according to claim 4, wherein the surface roughness of the modified base layer after the roughening treatment in step S1 is Ra0.1.
6. The stainless steel plate for cabinets of claim 4, wherein the thickness of the connection layer is 0.2-0.3 μm, and the thickness of the antibacterial layer is 0.3-0.5 μm.
7. The stainless steel plate for cabinets of claim 4, wherein the spraying pressure of the step S3 is 0.3-0.5 MPa.
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