CN112876980A - Antibacterial ultraviolet-curing writing coating composition and preparation method and application thereof - Google Patents
Antibacterial ultraviolet-curing writing coating composition and preparation method and application thereof Download PDFInfo
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- CN112876980A CN112876980A CN202110128829.XA CN202110128829A CN112876980A CN 112876980 A CN112876980 A CN 112876980A CN 202110128829 A CN202110128829 A CN 202110128829A CN 112876980 A CN112876980 A CN 112876980A
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
- B43L—ARTICLES FOR WRITING OR DRAWING UPON; WRITING OR DRAWING AIDS; ACCESSORIES FOR WRITING OR DRAWING
- B43L1/00—Repeatedly-usable boards or tablets for writing or drawing
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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
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses an antibacterial ultraviolet-curing writing coating composition and a preparation method and application thereof. The antibacterial ultraviolet curing writing coating composition comprises the following components: base material, photoinitiator, antibacterial agent and erasing auxiliary agent; wherein the base material comprises an acrylate resin prepolymer and an acrylate monomer; the erasing and writing auxiliary agent is fluorine-silicon co-modified polyacrylate resin. The paint film prepared from the coating composition provided by the invention has the characteristics of low odor, high surface hardness, excellent abrasion resistance, clear and non-shrinkage writing of a white board pen and long-time erasable after writing, and the coating also has high-efficiency antibacterial performance. The coating composition can be applied to preparing a writing film and an antibacterial writing board, has the characteristics of high hardness, high wear resistance, excellent writing adhesion and erasability and obvious antibacterial effect, and has wide market application prospect.
Description
Technical Field
The invention relates to the technical field of coatings, and particularly relates to an antibacterial ultraviolet-curing writing coating composition and a preparation method and application thereof.
Background
With the improvement of living standard, the requirements of people on the use experience of various products are higher and higher. The ultraviolet curing coating writing whiteboard is widely favored by various circles due to the excellent characteristics of fluent writing, durability, light weight, easy use, environmental protection and the like, and is widely used in occasions of teaching, office work, meetings, children intelligence development and the like.
Pathogenic bacteria such as escherichia coli, staphylococcus aureus, salmonella, candida, aspergillus niger and the like are quite common in daily life of people and can be basically called everywhere. There is a great threat to human health. In recent years, people have increased awareness and importance of pathogens. Antibacterial products such as antibacterial doorknobs and antibacterial tableware are popular.
CN111732906A discloses an antiviral and antibacterial functional film and a preparation method thereof, but the antibacterial film related to the scheme has no writing function. At present, all known writing board products have no antibacterial function, and the antibacterial writing board has great demand.
The most difficult technical point is how to solve the contradiction between writing adhesiveness (writing is smooth, ink shrinkage and broken lines are avoided) and erasability with time by using the ultraviolet curing coating technology to prepare the writing coating. At present, the main solution ideas include increasing the crosslinking density of the coating and reducing the surface tension of the coating. Silicone, organofluorine aids are common solutions to reduce the surface tension of coatings.
Both CN101481448A and CN101979449A disclose preparation methods of ultraviolet curing coatings for whiteboards (both have no antibacterial effect). The writing board coating in the scheme adopts the organic silicon resin or the organic silicon auxiliary agent to improve the erasing and writing performance, the substances have the characteristics of proper price but hydrophobicity and oleophylicity, have higher affinity to part of oily components (such as glycerin) in the white board pen ink, and easily cause the problem of writing residual oil marks when the white board pen is erased after writing. CN102131654A discloses a combined dry erase board/projection screen using fluorinated oligomers or fluorinated monomers to improve the erase and write performance, but these materials are generally expensive.
The method for synthesizing the fluorine-silicon co-modified light-cured acrylate resin comprises a free radical polymerization method, a silicon hydride addition method and the like. When the fluorine-silicon co-modified photocuring acrylic resin is synthesized by a free radical polymerization method, Si-O bonds can be damaged to different degrees, and the hydrophobic and oleophobic performances of the resin are influenced. The hydrosilylation method does not cause the defects, and the prepared material has more excellent performance. The silane coupling agent is grafted on the resin, so that the bonding fastness of the resin to partial base materials and the dispersing effect of the resin to certain inorganic fillers can be improved.
CN104974183A discloses a fluorosilicone acrylate and a preparation method thereof, wherein the technical scheme is that allyl acrylate reacts with hydrogen chlorosilane to prepare silicon-containing acrylate through hydrosilylation, and fluorine-containing alkyl magnesium bromide reacts with the silicon-containing acrylate to perform fluoroalkyl alkylation to obtain the fluorosilicone acrylate. The product obtained by the scheme has a plurality of fluoroalkyl groups in a dense packing state, and the poor writing ink shrinkage is easy to occur when the product is used for writing coating due to the excessively low surface energy.
Disclosure of Invention
The present invention is directed to solving at least one of the above problems in the prior art. Therefore, one object of the present invention is to provide an ultraviolet light-curable writing coating composition having an antibacterial function, another object of the present invention is to provide a method for preparing the antibacterial ultraviolet light-curable writing coating composition, and a third object of the present invention is to provide an application of the antibacterial ultraviolet light-curable writing coating composition.
The invention uses fluorine-silicon co-modification technology to improve the light-cured resin, wherein, the organosilicon is hydrophobic and oleophilic, and has defects in erasing and writing coating preparation, but the price is moderate; the organic fluorine is hydrophobic and oleophobic, has excellent erasing and writing effects, but is high in price. The fluorine-silicon co-modification is applied, so that advantages and disadvantages can be brought forward, the advantages of the fluorine-silicon co-modification and the fluorine-silicon co-modification are combined, and win-win effect is realized. The fluorine-silicon co-modified light-cured resin is applied to preparing a writing coating, and a good writing effect can be obtained.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides an antibacterial ultraviolet curing writing coating composition, which comprises the following components: base material, photoinitiator, antibacterial agent and erasing auxiliary agent;
the base material comprises an acrylate resin prepolymer and an acrylate monomer;
the erasing and writing auxiliary agent is fluorine-silicon co-modified polyacrylate resin.
According to some embodiments of the antibacterial uv-curable writing coating composition of the present invention, the antibacterial uv-curable writing coating composition comprises the following components in parts by mass: 25-55 parts of acrylate resin prepolymer, 12-48 parts of acrylate monomer, 2.5-8 parts of photoinitiator, 1-8 parts of antibacterial agent and 1-5 parts of erasing and writing auxiliary agent.
According to some embodiments of the antibacterial uv-curable writing coating composition of the present invention, the acrylate resin prepolymer comprises at least one of epoxy acrylate, urethane acrylate, polyester acrylate, and hyperbranched acrylate.
According to some preferred embodiments of the antibacterial uv-curable writing coating composition of the present invention, the acrylate resin prepolymer includes at least one of urethane acrylate having a functionality of not less than 3, epoxy acrylate having a functionality of not less than 2, and hyperbranched acrylate having a functionality of not less than 6.
According to some more preferred embodiments of the antibacterial UV-curable writing coating composition of the present invention, the acrylate resin prepolymer comprises at least one of Yangxing 6145-100, 6195-100, 621A-80, 6363, 6158B-80, DR-U195, Sandoma CN989, Bayer U400, B175X.
According to some embodiments of the antibacterial uv-curable writing coating composition of the present invention, the acrylate monomer comprises an acrylate monomer having a functionality of greater than or equal to 2.
According to some preferred embodiments of the antibacterial uv-curable writing coating composition of the present invention, the acrylate monomer comprises at least one of trimethylolpropane triacrylate (TMPTA), 1, 6-hexanediol diacrylate (HDDA), ethoxylated trimethylolpropane triacrylate (EO3TMPTA), dipentaerythritol hexaacrylate (DPHA), pentaerythritol triacrylate (PETA), propoxylated neopentyl glycol diacrylate (PONPGDA), polyethylene glycol (200) diacrylate (PEG (200) DA).
According to some embodiments of the antibacterial uv-curable writing coating composition of the present invention, the photoinitiator comprises at least one of a benzoin-based initiator, a benzil-based initiator, an alkyl phenone-based initiator, an acyl phosphorous oxide initiator, a benzophenone-based initiator, and a thioxanthone-based initiator.
According to some preferred embodiments of the antibacterial uv-curable writing coating composition of the present invention, the photoinitiator comprises at least one of 1-hydroxycyclohexyl phenyl ketone (photoinitiator 184), 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator 1173), 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (photoinitiator TPO).
According to some embodiments of the antimicrobial uv-curable writing coating composition of the present invention, the antimicrobial agent comprises at least one of a quaternary silicone based antimicrobial agent, a nano inorganic particle silver ion-loaded antimicrobial agent, a nano inorganic particle zinc ion-loaded antimicrobial agent.
According to some embodiments of the antibacterial uv-curable writing coating composition of the present invention, the erasure aids comprise the following preparation components in parts by mass: 8-12 parts of hydrogen-containing silicone oil, 3-8 parts of silane monomer, 20-55 parts of bifunctional (methyl) acrylate monomer, 1-3 parts of fluorine-containing (methyl) acrylate monomer and 7 x 10 parts of-4～1.5×10-3Catalyst and polymerization inhibitor in 0.3-0.6 weight portions.
Wherein the difunctional (meth) acrylate monomer means a difunctional acrylate monomer and/or a difunctional methacrylate monomer; the fluorine-containing (meth) acrylate monomer means a fluorine-containing acrylate monomer and/or a fluorine-containing methacrylate monomer.
According to some embodiments of the erasure assistant of the present invention, the hydrogen content of the hydrogen-containing silicone oil is 1.05 wt% to 1.4 wt%.
According to some embodiments of the erasure aids of the present invention, the silane monomer includes at least one of vinyltrimethoxysilane, vinyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropyltriethoxysilane.
According to some embodiments of the erasure aids of the present invention, the difunctional (meth) acrylate monomer includes at least one of ethylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate.
According to some preferred embodiments of the erasure aids of the present invention, the difunctional (meth) acrylate monomer includes at least one of 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate.
According to some embodiments of the erasure aids of the present invention, the fluorine-containing (meth) acrylate monomer includes at least one of trifluoroethyl (meth) acrylate, hexafluorobutyl (meth) acrylate, dodecafluoroheptyl (meth) acrylate, and tridecafluorooctyl (meth) acrylate.
According to some preferred embodiments of the erasure aids of the present invention, the fluorine-containing (meth) acrylate monomer includes at least one of trifluoroethyl methacrylate, hexafluorobutyl methacrylate, dodecafluoroheptyl acrylate, and tridecafluoroctyl acrylate.
According to some embodiments of the write-once additive of the present invention, the catalyst is a platinum-based catalyst.
According to some preferred embodiments of the erasure assistant of the present invention, the catalyst is chloroplatinic acid.
According to some embodiments of the write-once additive of the present invention, the catalyst is prepared as a catalyst solution. In some embodiments of the invention, the catalyst solution is an isopropyl chloroplatinate solution.
According to some embodiments of the erasure aids of the present invention, the polymerization inhibitor comprises at least one of p-hydroxyanisole, hydroquinone, p-benzoquinone, methylhydroquinone, phenothiazine, 2, 5-di-tert-butylhydroquinone, 2-tert-butylhydroquinone.
According to some embodiments of the erasure assistant of the present invention, the erasure assistant is prepared from the following components, wherein the molar ratio of carbon-carbon double bonds (C ═ C bonds) to silicon-hydrogen bonds (Si — H bonds) is (2.1 to 2.4): 1.
according to some embodiments of the antibacterial uv-curable writing coating composition of the present invention, the method for preparing the erasure aids comprises the steps of:
1) mixing hydrogen-containing silicone oil, a silane monomer, a fluorine-containing (methyl) acrylate monomer and a polymerization inhibitor, heating, adding a part of catalyst, and reacting;
2) and continuously adding the residual catalyst and the bifunctional (methyl) acrylate monomer for reaction to obtain the erasing and writing auxiliary agent.
According to some embodiments of the process for the preparation of the erasure aids of the present invention, the preparation process is carried out under a protective atmosphere. In some embodiments of the invention, the shielding gas is nitrogen.
According to some embodiments of the method for preparing an erasure assistant, in step 1), the heating temperature is 80 ℃ to 110 ℃.
According to some embodiments of the method for preparing an erasure assistant of the present invention, in step 1), the partial catalyst is a catalyst added in an amount of 20% to 72% of the total catalyst ratio.
According to some preferred embodiments of the method for preparing an erasure assistant of the present invention, in step 1), the partial catalyst is added in an amount of 40% to 50% of the total catalyst ratio.
According to some embodiments of the method for preparing an erasure assistant of the present invention, in the step 1), a catalyst solution is added during heating. In some embodiments of the invention, the catalyst solution is added for a period of time ranging from 1 hour to 3 hours; the catalyst solution is chloroplatinic acid isopropanol solution; the addition mode is dropwise.
According to some embodiments of the method for preparing an erasure assistant of the present invention, in the step 1), the reaction is performed at 80 ℃ to 110 ℃ for 3 hours to 7 hours.
According to some embodiments of the method for preparing an erasure assistant, in the step 2), the temperature of the reaction system is adjusted to 80-90 ℃, and then the rest of the catalyst and the bifunctional (meth) acrylate monomer are continuously added.
According to some embodiments of the process for preparing an erasure assistant of the present invention, 3 × 10 is added in step 1)-4～5×10-4The catalyst is added by 4 multiplied by 10 in the step 2)-4～1×10-3Parts by mass of a catalyst.
According to some embodiments of the method for preparing an erasure assistant according to the present invention, in the step 2), the time for continuously adding the remaining catalyst and the bifunctional (meth) acrylate monomer is 0.5 to 1.5 hours. In some embodiments of the invention, the addition of the remaining catalyst and difunctional (meth) acrylate monomer is by dropwise addition.
According to some embodiments of the process for preparing an erasure assistant in the present invention, in the step 2), a sample is taken during the reaction for infrared testing, and when the infrared spectrum of the product is 2167cm-1When the absorption peak (Si-H bond stretching vibration) disappears, the reaction end point is determined.
According to some embodiments of the antibacterial uv-curable writing coating composition of the present invention, the components of the antibacterial uv-curable writing coating composition further comprise a leveling agent and/or a diluent.
According to some embodiments of the antibacterial ultraviolet-curable writing coating composition of the present invention, when the components of the antibacterial ultraviolet-curable writing coating composition further include a leveling agent, the mass part of the leveling agent is 0.1 to 0.5 parts.
According to some embodiments of the antibacterial uv-curable writing coating composition of the present invention, the leveling agent comprises at least one of an acrylate-based leveling agent, a silicone-based leveling agent, and a fluorocarbon-based leveling agent.
According to some preferred embodiments of the antibacterial uv-curable writing coating composition of the present invention, the leveling agent comprises at least one of BYK358, BYK354, BYK361, TEGO300, MODAFLOW 9200.
According to some embodiments of the antibacterial ultraviolet-curable writing coating composition of the present invention, when the components of the antibacterial ultraviolet-curable writing coating composition further include a diluent, the mass part of the diluent is 0 to 30 parts. Thus, by adding the diluent, the construction can be facilitated.
According to some embodiments of the antibacterial uv-curable writing coating composition of the present invention, the diluent comprises at least one of isopropyl alcohol, propyl alcohol, n-butanol, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, diacetone alcohol, ethylene glycol ethyl ether, propylene glycol monomethyl ether.
A second aspect of the present invention provides a method for preparing the antibacterial uv-curable writing coating composition according to the first aspect of the present invention, comprising the steps of: the components are mixed and filtered to obtain the antibacterial ultraviolet curing writing coating composition.
According to some embodiments of the method for preparing the antibacterial ultraviolet-curable writing coating composition, when the antibacterial agent is an organosilicon quaternary ammonium salt antibacterial agent, the specific preparation method is as follows: and adding the antibacterial agent, the leveling agent (or no leveling agent) and the erasing and writing auxiliary agent into the acrylate monomer for dispersion, then adding the acrylate prepolymer for dispersion, then adding the photoinitiator for continuous dispersion, and filtering to obtain the antibacterial ultraviolet curing writing coating composition.
According to some embodiments of the method for preparing the antibacterial ultraviolet-curable writing coating composition, when the antibacterial agent contains a nano inorganic particle silver ion-loaded antibacterial agent and/or a nano inorganic particle zinc ion-loaded antibacterial agent, the specific preparation method is as follows: and adding the antibacterial agent and the erasing and writing auxiliary agent into the acrylate monomer for dispersing, grinding, adding the acrylate prepolymer and the leveling agent (or no leveling agent) for dispersing, then adding the photoinitiator for continuously dispersing, and filtering to obtain the antibacterial ultraviolet curing writing coating composition. In some embodiments of the invention, the milling is to a particle size of less than 0.5 microns; the grinding is carried out by a horizontal sand mill with a grinding medium of 0.3mm zirconium balls.
According to some embodiments of the method of making an antimicrobial uv-curable writing coating composition of the present invention, the addition of the photoinitiator continues the dispersion until the photoinitiator is completely dissolved.
According to some embodiments of the method of making an antimicrobial uv-curable writing coating composition of the present invention, the filtering is through a 1 micron filter unit. In some embodiments of the invention, the filtration is a bag filter with a filtration precision of 1 micron.
A third aspect of the present invention provides a coating layer formed from the antibacterial uv-curable writing coating composition according to the first aspect of the present invention.
The fourth aspect of the present invention provides a writing film comprising a base film and a coating layer provided on a surface of the base film; the coating is formed from an antibacterial uv-curable writing coating composition according to the first aspect of the present invention.
According to some embodiments of the writing film of the present invention, the base film is at least one of a PET (polyethylene terephthalate) film, a PE (polyethylene) film, a PP (polypropylene) film, a PVC (polyvinyl chloride) film.
According to some embodiments of the writing film of the present invention, the base film has a thickness of 100 to 200 micrometers.
According to some preferred embodiments of the writing film of the present invention, the base film has a thickness of 125 to 175 micrometers.
According to some embodiments of the writing film of the present invention, the coating has a thickness of 3 to 8 microns.
According to some preferred embodiments of the writing film of the present invention, the coating layer has a thickness of 4 to 6 micrometers.
According to some embodiments of the writing film of the present invention, the coating has a hardness of 1H or more, as measured by the GB/T6739 & 2006 paint film hardness by pencil method.
According to some embodiments of the writing film of the present invention, the writing film is formed by coating an antibacterial uv-curable writing coating composition on a base film. Suitable coating means include dip coating, roll coating, curtain coating, spray coating, gravure coating or gravure coating, preferably gravure coating.
According to some embodiments of the writing film of the present invention, the coating forming method of the writing film is uv curing. In some embodiments of the invention, the writing film is formed by a coating process using a mercury lamp.
The fifth aspect of the present invention provides a writing board, comprising a magnetic material and a writing film provided on a surface of the magnetic material; the writing film according to the fourth aspect of the present invention. Thus, the writing board is a magnetic-absorption antibacterial writing board.
According to some embodiments of the writing tablet of the present invention, the magnetic material comprises at least one of a permanent magnetic material, a soft magnetic material.
According to some embodiments of the invention, the permanent magnetic material comprises at least one of an alnico series permanent magnetic alloy, an iron-cobalt series permanent magnetic alloy, a permanent magnetic ferrite, a rare earth permanent magnetic material.
According to some embodiments of the invention, the soft magnetic material comprises at least one of pure iron, iron-silicon based alloys, iron-aluminum based alloys, iron-silicon-aluminum based alloys, nickel-iron based alloys, iron-cobalt based alloys, soft magnetic ferrite, amorphous soft magnetic alloys, microcrystalline soft magnetic alloys, nanocrystalline soft magnetic alloys.
According to some embodiments of the tablet of the present invention, the magnetic material is formed from a magnetic iron powder slurry, or a ferromagnetic diaphragm.
According to some embodiments of the writing board of the present invention, the magnetic iron powder paste is directly compounded with the writing film through a coating, silk-screen or spraying process.
According to some embodiments of the writing board of the present invention, the ferromagnetic film is compounded with the writing film by extrusion, casting, calendering or laminating.
The invention has the beneficial effects that:
the paint film prepared from the coating composition provided by the invention has the characteristics of low odor, high surface hardness, excellent abrasion resistance, clear and non-shrinkage writing of a white board pen and long-time erasable after writing, and the coating also has high-efficiency antibacterial performance. The coating composition can be applied to preparing a writing film, the writing film is combined with a magnetic material, a writing board product with a magnetic attraction function and an antibacterial function can be obtained, and the market application prospect is wide.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials, reagents or apparatus used in the examples and comparative examples were obtained from conventional commercial sources or can be obtained by a method of the prior art, unless otherwise specified. Unless otherwise indicated, the testing or testing methods are conventional in the art.
The amounts of "parts" used in the following examples are "parts by mass" unless otherwise specified.
Example 1
In a four-neck round-bottom flask provided with a mechanical stirrer, a reflux condenser tube, a constant-pressure dropping funnel and a nitrogen inlet tube, 10 parts of low-hydrogen silicone oil (hydrogen content is 1.2 percent), 7 parts of vinyl trimethoxy silane coupling agent, 3 parts of trifluoroethyl methacrylate and 0.32 part of polymerization inhibitor are sequentially added after vacuumizing and nitrogen charging are repeated for 3 times, the mixture is heated to 85 ℃ under the condition of nitrogen protection, and 400 multiplied by 10 of hydrogen content is dropped in the heating process-6The catalyst solution of chloroplatinic acid (chloroplatinic acid isopropanol solution) was added dropwise over 1.5 hours. After the dropwise addition, the reaction is continued for 4 hours under the condition of heat preservation. After the heat preservation reaction is finished, the temperature is raised to 90 ℃, and 25 parts of 1, 6-hexanediol diacrylate monomer and chloroplatinic acid isopropanol solution (containing 400 multiplied by 10) are dripped-6Parts of chloroplatinic acid) is added in 0.5h, and the reaction is continued after the addition is finished. Second heat preservationSampling after reacting for 3h, performing infrared test, and obtaining a product with the infrared spectrum of 2167cm-1The absorption peak (Si-H bond stretching vibration) disappears, and the heating is stopped. Cooling to room temperature, and removing solvent to obtain colorless transparent liquid to obtain erasing and writing assistant 1 #.
Example 2
In a four-neck round-bottom flask provided with a mechanical stirrer, a reflux condenser tube, a constant pressure dropping funnel and a nitrogen inlet tube, 12 parts of low hydrogen silicone oil (hydrogen content is 1.4%), 5.2 parts of gamma-methacryloxypropyl trimethoxy siloxane, 2 parts of hexafluorobutyl methacrylate and 0.5 part of polymerization inhibitor are sequentially added after vacuumizing and nitrogen filling are repeated for 3 times, the mixture is heated to 100 ℃ under the condition of nitrogen protection, and 450 multiplied by 10 of the total weight of the mixture is dripped in the heating process-6And (4) dropwise adding the catalyst solution (chloroplatinic acid isopropanol solution) of chloroplatinic acid for 2 hours. After the dropwise addition, the reaction is continued for 4 hours under the condition of heat preservation. After the heat preservation reaction is finished, 50 parts of tripropylene glycol diacrylate monomer and a chloroplatinic acid isopropanol solution (containing 1000 multiplied by 10) are added dropwise when the temperature is adjusted to 90 DEG C-6Parts of chloroplatinic acid) is added in 1.5h, and then the reaction is kept at 90 ℃ after the addition is finished. Sampling for infrared test after the second heat preservation reaction for 4 hours, and 2167cm in infrared spectrum of the product-1The absorption peak (Si-H bond stretching vibration) disappears, and the heating is stopped. Cooling to room temperature, and removing solvent to obtain colorless transparent liquid, to obtain erasing and writing auxiliary agent No. 2.
Example 3
In a four-neck round-bottom flask provided with a mechanical stirrer, a reflux condenser tube, a constant pressure dropping funnel and a nitrogen inlet tube, 11 parts of low hydrogen silicone oil (hydrogen content 1.1 percent), 3.8 parts of gamma-methacryloxypropyl trimethoxy siloxane, 1.5 parts of dodecafluoroheptyl acrylate and 0.4 part of polymerization inhibitor are sequentially added after vacuumizing and nitrogen filling are repeated for 3 times, the mixture is heated to 105 ℃ under the protection of nitrogen, and 500 multiplied by 10 of hydrogen is dropwise added in the heating process-6And (4) dropwise adding a platinum catalyst solution (chloroplatinic acid isopropanol solution) of chloroplatinic acid for 2 hours. After the dropwise addition, the reaction is continued for 6 hours under the condition of heat preservation. After the heat preservation reaction is finished, 26 parts of neopentyl glycol diacrylate monomer and a chloroplatinic acid isopropanol solution (containing 500 multiplied by 10) are dripped into the mixture after the temperature is adjusted to 85 DEG C-6Parts of chloroplatinic acid), 0.8h of dropsAfter the addition is finished, the reaction is kept under the temperature after the dripping is finished. Sampling for infrared test after the second heat preservation reaction for 3 hours, and 2167cm in infrared spectrum of the product-1The absorption peak (Si-H bond stretching vibration) disappears, and the heating is stopped. Cooling to room temperature, and removing solvent to obtain colorless transparent liquid to obtain erasing and writing assistant No. 3.
Example 4
In a four-neck round-bottom flask provided with a mechanical stirrer, a reflux condenser tube, a constant pressure dropping funnel and a nitrogen inlet tube, 9 parts of low hydrogen silicone oil (hydrogen content is 1.32 percent), 6 parts of gamma-methacryloxypropyl trimethoxy siloxane, 1.2 parts of tridecyl acrylate monomer and 0.45 part of polymerization inhibitor are sequentially added after vacuumizing and nitrogen filling are repeated for 3 times, the mixture is heated to 110 ℃ under the condition of nitrogen protection, and 600 multiplied by 10 of the total weight of the mixture is dripped during the heating process-6The catalyst solution of chloroplatinic acid (chloroplatinic acid isopropanol solution) was added dropwise over 2.5 hours. After the dropwise addition, the reaction is continued for 6 hours under the condition of heat preservation. After the heat preservation reaction is finished, adjusting the temperature to 90 ℃, and dropwise adding 35 parts of polyethylene glycol (200) diacrylate monomer and chloroplatinic acid isopropanol solution (containing 700 multiplied by 10)-6Parts of chloroplatinic acid) is added in 1 hour, and the reaction is continued after the addition is finished. Sampling for infrared test after the second heat preservation reaction for 3.5 hours, and 2167cm in infrared spectrum of the product-1The absorption peak (Si-H bond stretching vibration) disappears, and the heating is stopped. Cooling to room temperature, and removing solvent to obtain yellowish transparent liquid as erasing and writing assistant No. 4.
Example 5
In a four-neck round bottom flask provided with a mechanical stirrer, a reflux condenser tube, a constant pressure dropping funnel and a nitrogen inlet tube, 10.8 parts of low hydrogen silicone oil (hydrogen content is 1.1 percent) after vacuumizing and nitrogen charging are repeated for 3 times, 5 parts of gamma-methacryloxypropyltriethoxysilane, 2 parts of hexafluorobutyl methacrylate, 0.8 part of dodecafluoroheptyl acrylate monomer and 0.4 part of polymerization inhibitor are sequentially added, the mixture is heated to 100 ℃ under the protection of nitrogen, and 400 multiplied by 10 is dripped in the heating process-6And (4) dropwise adding the catalyst solution (chloroplatinic acid isopropanol solution) of chloroplatinic acid for 2 hours. After the dropwise addition, the reaction is continued for 5 hours under the condition of heat preservation. After the heat preservation reaction is finished, the temperature is adjusted to 90 ℃, and tripropylene glycol dipropylene glycol is dripped38 parts of acid ester monomer and chloroplatinic acid isopropanol solution (containing 800X 10)-6Parts of chloroplatinic acid) is added in 1.5h, and then the reaction is continued to be kept warm after the addition is finished. Sampling for infrared test after the second heat preservation reaction for 4 hours, and 2167cm in infrared spectrum of the product-1The absorption peak (Si-H bond stretching vibration) disappears, and the heating is stopped. Cooling to room temperature, and removing solvent to obtain colorless transparent liquid, to obtain erasing and writing auxiliary agent No. 5.
Example 6
The coating composition of this example comprises the following raw materials:
the preparation method of the coating liquid comprises the following steps: adding 1.8 parts of organosilicon quaternary ammonium salt antibacterial agent, 0.15 part of Tego300 and 1.2 parts of erasing auxiliary agent 4# into a mixture of 12 parts of TMPTA and 6 parts of HDDA, adding 25 parts of 6145-100 and 8 parts of CN989 after high-speed uniform dispersion, and adding 4 parts of photoinitiator 184 after high-speed uniform dispersion to continue dispersion until no particulate exists. Filtering with a bag filter with the filtering precision of 1 mu m to obtain the antibacterial writing coating.
The obtained coating is diluted to construction viscosity by ethyl acetate, coated on a white PVC film of 175 microns by a 120-line micro-concave stick, the thickness of the dry film of the coating is 5 microns, and the antibacterial writing film is obtained after the coating is solidified by a high-pressure mercury lamp.
And (3) cold mounting the obtained antibacterial writing film on the surface of a ferromagnetic diaphragm material by using an acrylic acid adhesive to obtain the antibacterial writing board 1.
Example 7
The coating composition of this example comprises the following raw materials:
the preparation method of the coating liquid comprises the following steps: 6 parts of organosilicon quaternary ammonium salt antibacterial agent, 0.5 part of BYK358 and 4 parts of erasing and writing auxiliary agent 2# are added into a mixture of 15 parts of EO3TMPTA and 12 parts of HDDA, after the mixture is uniformly dispersed at a high speed, 25 parts of 6145-doped 100, 15 parts of 6195 and 8 parts of CN989 are added, and after the mixture is uniformly dispersed at a high speed, 4 parts of photoinitiator 1173 and 2 parts of photoinitiator 184 are added for continuous dispersion until no particulate exists. Filtering with a bag filter with the filtering precision of 1 mu m to obtain the antibacterial writing coating.
The obtained coating is diluted to construction viscosity by ethyl acetate, coated on a 150-micron white pretreated PP film by a 120-line micro-concave stick, the thickness of a coating dry film is 5 mu m, and the antibacterial writing film is obtained after the coating is cured by a high-pressure mercury lamp.
The obtained antibacterial writing film is thermally adhered to the surface of the ferromagnetic diaphragm material by using acrylic acid hot melt adhesive to obtain the antibacterial writing board 2.
Example 8
The coating composition of this example comprises the following raw materials:
the preparation method of the coating liquid comprises the following steps: adding 4 parts of nano inorganic particle silver ion-loaded antibacterial agent and 3 parts of erasing and writing auxiliary agent 5# into a mixture of 12 parts of PETA and 6 parts of HDDA, circularly grinding the mixture to a particle size of less than 0.5 mu m by using a horizontal sand mill (a grinding medium is a 0.3mm zirconium ball) after high-speed pre-dispersion, then discharging the mixture, adding 25 parts of DPHA, 15 parts of U400, 12 parts of B175X and 0.3 part of BYK358, uniformly dispersing the mixture at a high speed, adding 2.5 parts of photoinitiator 184 and 0.5 part of photoinitiator TPO, and continuously dispersing the mixture until the photoinitiator is completely dissolved. Filtering with a bag filter with the filtering precision of 1 mu m to obtain the antibacterial writing coating.
The obtained coating is diluted to construction viscosity by using a mixture of ethyl acetate and butyl acetate in a mass ratio of 2:1, the coating is coated on a 125-micron PET film by using a 120-line micro-concave stick, the thickness of a dry film of the coating is 4 mu m, and the antibacterial writing film is obtained after the coating is cured by a high-pressure mercury lamp.
The obtained antibacterial writing film is pasted to a ferromagnetic diaphragm material by using a double-component polyurethane composite adhesive to obtain the antibacterial writing board 3.
Example 9
The coating composition of this example comprises the following raw materials:
the preparation method of the coating liquid comprises the following steps: adding 3 parts of nano inorganic particle silver ion-loaded antibacterial agent and 2.5 parts of erasing auxiliary agent 3# into a mixture of 8 parts of TMPTA and 5 parts of PONPGDA, circularly grinding the mixture to a particle size of less than 0.5 mu m by using a horizontal sand mill (grinding medium is a zirconium ball with 0.3 mm) after high-speed pre-dispersion, then discharging the mixture, adding 25 parts of 6145-100, 12 parts of 621A-80, 5 parts of 6363 and 0.3 part of MODAFLOW9200, adding 3 parts of photoinitiator 184, 1 part of photoinitiator 1173 and 0.3 part of photoinitiator TPO after high-speed uniform dispersion, and continuing dispersion until the photoinitiators are completely dissolved. Filtering with a bag filter with the filtering precision of 1 mu m to obtain the antibacterial writing coating.
The obtained coating is diluted to construction viscosity by using a mixture of ethyl acetate and butyl acetate in a mass ratio of 2:1, the coating is coated on a 125-micron PET film by using a 120-line micro-concave stick, the thickness of a dry film of the coating is 5 mu m, and the antibacterial writing film is obtained after the coating is cured by a high-pressure mercury lamp.
And combining the magnetic iron powder slurry with the obtained antibacterial writing film through a coating process to obtain the antibacterial writing board 4.
Example 10
The coating composition of this example comprises the following raw materials:
the preparation method of the coating liquid comprises the following steps: adding 3 parts of organosilicon quaternary ammonium salt antibacterial agent, 0.3 part of Tego300, 2.5 parts of erasing auxiliary agent 5# into 12 parts of HDDA, adding 30 parts of 621A-80, 15 parts of 6158B-80 and 8 parts of 6145-100 after high-speed uniform dispersion, adding 3 parts of photoinitiator 184, 2 parts of photoinitiator 1173 and 0.3 part of photoinitiator TPO after high-speed uniform dispersion, and continuing dispersion until no particulate exists. Filtering with a bag filter with the filtering precision of 1 mu m to obtain the antibacterial writing coating.
The obtained coating is diluted to construction viscosity by using a mixture of ethyl acetate, butyl acetate, toluene and diacetone alcohol in a mass ratio of 2:1:1:0.3, the coating is coated on a 125-micron PET film by using a 120-line micro-concave stick, the thickness of a dry film of the coating is 3 mu m, and the antibacterial writing film is obtained after the coating is cured by a high-pressure mercury lamp.
And combining the magnetic iron powder slurry with the obtained antibacterial writing film through a spraying process to obtain the antibacterial writing board 5.
Example 11
The coating composition of this example comprises the following raw materials:
the preparation method of the coating liquid comprises the following steps: adding 3 parts of nano inorganic particle zinc ion-loaded antibacterial agent and 4.8 parts of erasing assistant 1# into a mixture of 30 parts of PETA, 12 parts of HDDA and 8 parts of PONPGDA, circularly grinding the mixture to a particle size of less than 0.5 mu m by using a horizontal sand mill (a grinding medium is a 0.3mm zirconium ball) after high-speed pre-dispersion, then discharging the mixture, adding 4 parts of organosilicon quaternary ammonium salt antibacterial agent, 25 parts of 6195-100, 15 parts of DR-U195 and 0.5 part of Tego300, adding 5 parts of photoinitiator 1173 and 2 parts of photoinitiator 184 after high-speed uniform dispersion, and continuing dispersion until the photoinitiator is completely dissolved. The antibacterial writing coating paint is obtained by filtering with a bag filter with the filtering precision of 1 mu m.
The obtained coating is coated on a 125-micron PET film by using a 150-line micro-concave stick, the thickness of a dry film of the coating is 6 mu m, and the antibacterial writing film is obtained after the coating is cured by a high-pressure mercury lamp.
The obtained antibacterial writing film is pasted on the surface of a ferromagnetic diaphragm material by using acrylic acid hot melt adhesive to obtain the antibacterial writing board 6.
Comparative example 1
The coating composition of this example comprises the following raw materials:
the preparation method of the coating liquid comprises the following steps: adding 0.5 part of Tego300 into a mixture of 15 parts of TPGDA, 12 parts of HDDA and 8 parts of TMPTA, adding 25 parts of 611B-85 and 15 parts of 621A-80 after uniformly dispersing at a high speed, adding 5 parts of photoinitiator 1173 and 4 parts of photoinitiator 184 after uniformly dispersing at a high speed, and continuing dispersing until no particulate matter exists. The writing coat paint was obtained after filtration using a bag filter having a filtration accuracy of 1 μm.
The obtained coating was diluted with ethyl acetate to an application viscosity, and then coated on a 75 μm PET film with a 150-line micro-gravure, the thickness of the dry film of the coating being 5 μm, and the writing film was obtained after curing with a high-pressure mercury lamp.
The obtained writing film was pasted to a ferromagnetic film material using an acrylic hot melt adhesive to obtain a writing board 7.
Comparative example 2
The coating composition of this example comprises the following raw materials:
the preparation method of the coating liquid comprises the following steps: adding 0.8 part of organosilicon quaternary ammonium salt antibacterial agent and 0.5 part of Tego300 into a mixture of 15 parts of DPHA and 12 parts of PETA, uniformly dispersing at a high speed, adding 25 parts of 6145-100, 15 parts of erasing and writing auxiliary agent 4#, and 12 parts of 621A-80, uniformly dispersing at a high speed, adding 5 parts of photoinitiator 184, and continuously dispersing until no particulate exists. The writing coat paint was obtained after filtration using a bag filter having a filtration accuracy of 1 μm.
The obtained coating was coated on a 75 μm PET film using a 150-line gravure, and the dry film thickness of the coating was 12 μm, and a writing film was obtained after curing by a high-pressure mercury lamp.
The obtained writing film is pasted to the surface of the ferromagnetic diaphragm material by using acrylic acid hot melt adhesive to obtain the writing board 8.
The performance of the writing board products 1-6 obtained in examples 6-11 and the writing board products 7-8 obtained in comparative examples 1-2 were tested, and the test results are shown in table 1.
TABLE 1 writing board product Performance test results
The performance test methods in table 1 are:
(1) gloss: measured by using a 60-degree angle gloss meter with the model of MG-60 provided by Shanghai Lichen West instruments science and technology Limited.
(2) Coating adhesion: refer to the national Standard GB/T9286 1998 test for marking paint and varnish paint films.
(3) Coating pencil hardness: the hardness of the paint film is determined by referring to the national standard GB/T6739-2006 color paint and varnish pencil method.
(4) Writing adhesion: refer to the trade standard QB/T4153-. The 'check mark' represents that the writing hand feeling is smooth, the handwriting is uniform, the lines are obvious and no broken line exists; "Δ" indicates that there was slight shrinkage at the edge of the written handwriting, but the line was still clear and there was no broken line; "X" indicates that the written handwriting shrinks remarkably, has obvious line breakage and even shrinks into ink dots.
(5) Wear resistance of the coating: refer to the trade standard QB/T4153-. The symbol represents that the writing and wiping functions of the writing surface are normal after the test; "X" represents that there were defects such as scratches and ink marks remaining on the writing surface after the test.
(6) Erasability: the test was carried out using method A as shown in Standard 5.3.2.2, with reference to the trade Standard QB/T4153-2010 whiteboard. The symbol represents that no writing residue exists on the writing surface after the test; "X" indicates that writing was left on the writing surface after the test.
(7) The antibacterial effect is as follows: the test is carried out according to the national standard GB/T31402-2015 plastic product surface antibacterial property test method, and the test strain is escherichia coli. The antibacterial activity value is more than or equal to 2, and the antibacterial rate is more than or equal to 99 percent, so that the antibacterial effect is realized.
As can be seen from the test results in Table 1, the writing board products obtained in examples 6 to 11 were characterized by high hardness, high abrasion resistance, excellent writing adhesion and erasability, and remarkable antibacterial effect. Comparative example 1 because the coating formulation main body is low-functionality polyurethane resin, the coating hardness is low, the wearability is poorer, and because the erasing auxiliary agent is not added, the product has very good writing adhesiveness, but the erasability can not meet the use requirement, in addition, because the antibacterial agent is not added, the product has no antibacterial effect; comparative example 2 coating thickness is too thick, resulting in too large curing shrinkage and brittleness of the coating, affecting the adhesion of the coating, and due to too much addition of the erasing and writing assistant and too low surface energy of the coating, writing shrinkage after writing is serious, and the use requirement of a writing board cannot be met, and in addition, due to too low addition of the antibacterial agent, the antibacterial effect cannot meet the requirement.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. An antibacterial ultraviolet-curable writing coating composition, which is characterized in that: comprises the following components: base material, photoinitiator, antibacterial agent and erasing auxiliary agent;
the base material comprises an acrylate resin prepolymer and an acrylate monomer;
the erasing and writing auxiliary agent is fluorine-silicon co-modified polyacrylate resin.
2. The antibacterial uv-curable writing coating composition according to claim 1, wherein: the adhesive comprises the following components in parts by mass: 25-55 parts of acrylate resin prepolymer, 12-48 parts of acrylate monomer, 2.5-8 parts of photoinitiator, 1-8 parts of antibacterial agent and 1-5 parts of erasing and writing auxiliary agent.
3. The antibacterial uv-curable writing coating composition according to claim 1 or 2, wherein: the acrylate resin prepolymer comprises at least one of epoxy acrylate, polyurethane acrylate, polyester acrylate and hyperbranched acrylate; the acrylate monomer comprises an acrylate monomer with the functionality of more than or equal to 2; the antibacterial agent comprises at least one of an organosilicon quaternary ammonium salt antibacterial agent, a nano inorganic particle silver ion-loaded antibacterial agent and a nano inorganic particle zinc ion-loaded antibacterial agent.
4. The antibacterial uv-curable writing coating composition according to claim 1 or 2, wherein: the erasing and writing auxiliary agent comprises the following preparation components in parts by mass: 8-12 parts of hydrogen-containing silicone oil, 3-8 parts of silane monomer, 20-55 parts of bifunctional (methyl) acrylate monomer, 1-3 parts of fluorine-containing (methyl) acrylate monomer and 7 x 10 parts of-4～1.5×10-3Catalyst and polymerization inhibitor in 0.3-0.6 weight portions.
5. The antibacterial UV-curable writing coating composition according to claim 4, wherein: the preparation method of the erasing and writing auxiliary agent comprises the following steps:
1) mixing hydrogen-containing silicone oil, a silane monomer, a fluorine-containing (methyl) acrylate monomer and a polymerization inhibitor, heating, adding a part of catalyst, and reacting;
2) and continuously adding the residual catalyst and the bifunctional (methyl) acrylate monomer for reaction to obtain the erasing and writing auxiliary agent.
6. The antibacterial uv-curable writing coating composition according to claim 1 or 2, wherein: the components of the antibacterial ultraviolet curing writing coating composition also comprise a leveling agent and/or a diluting agent.
7. A method for preparing the antibacterial uv-curable writing coating composition according to any one of claims 1 to 6, characterized in that: the method comprises the following steps: the components are mixed and filtered to obtain the antibacterial ultraviolet curing writing coating composition.
8. A coating, characterized by: the coating layer is formed of the antibacterial uv-curable writing coating composition of any one of claims 1 to 6.
9. A writing film characterized by: comprises a base film and a coating layer arranged on the surface of the base film; the coating layer is formed of the antibacterial uv-curable writing coating composition of any one of claims 1 to 6.
10. A writing board characterized by: the magnetic writing film comprises a magnetic material and a writing film arranged on the surface of the magnetic material; the writing film of claim 9.
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| CN115717027A (en) * | 2022-11-30 | 2023-02-28 | 苏州微介面材料科技有限公司 | Anti-scratch magnetic suction writing wall |
| CN116042083A (en) * | 2022-12-21 | 2023-05-02 | 长飞光纤光缆股份有限公司 | Silane modified low-refractive-index optical fiber coating |
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