CN111635700A - Efficient anti-cracking polishing solution and using method thereof - Google Patents
Efficient anti-cracking polishing solution and using method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B29/00—Machines or devices for polishing surfaces on work by means of tools made of soft or flexible material with or without the application of solid or liquid polishing agents
- B24B29/005—Machines or devices for polishing surfaces on work by means of tools made of soft or flexible material with or without the application of solid or liquid polishing agents using brushes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B57/00—Devices for feeding, applying, grading or recovering grinding, polishing or lapping agents
- B24B57/02—Devices for feeding, applying, grading or recovering grinding, polishing or lapping agents for feeding of fluid, sprayed, pulverised, or liquefied grinding, polishing or lapping agents
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4808—Mixtures of two or more polyetherdiols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
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Abstract
The invention relates to the technical field of ceramic tile polishing, in particular to a high-efficiency anti-cracking polishing solution and a using method thereof. The preparation raw materials comprise 10-30 parts by weight of silica sol, 0.5-2 parts by weight of auxiliary agent, 0.1-3 parts by weight of dispersing agent, 1-5 parts by weight of super elastic polymer and 60-80 parts by weight of water; the preparation method of the super elastic polymer comprises the following steps: (1) adding 3.0mmol of MDI and 0.8-2.0 mmol of polyol into 20ml of DMAc, and reacting at 80 ℃ for 2-4 hours to obtain an intermediate A; (2) and cooling the intermediate A to room temperature, dropwise adding ethylenediamine while stirring, heating to 70 ℃, reacting for 4 hours, and concentrating to obtain the intermediate. The polishing solution can obviously improve the adhesion and the bonding strength of the polishing solution to the surface of the ceramic tile, and can also obviously improve the cracking and the wrinkling of an antifouling layer formed by the polishing solution on the surface of the ceramic tile under the high-low temperature alternation, so that the antifouling layer still keeps good coating integrity and good glossiness in a severe environment.
Description
Technical Field
The invention relates to the technical field of ceramic tile polishing, in particular to a high-efficiency anti-cracking polishing solution and a using method thereof.
Background
The polished tiles are popular with consumers once coming out, and have clean and beautiful appearance, so that the polished tiles are the main products for decorating floors and hallways of markets and civil houses, and are commonly used on the surfaces of articles such as floors, walls, dining tables, office tables and the like. However, since a large amount of air holes and fine lines are generated inside and on the surface of the ceramic tile in the production process of the ceramic tile, although some air holes on the surface of the ceramic tile can be eliminated through sintering, closed air holes inside the ceramic tile are exposed on the surface of the ceramic tile in subsequent polishing, grinding and other processes to form open air holes which are easy to store dirt and contain dirt, and the ceramic tile is easy to be contaminated with pollutants such as ink, paint, tea water, foot prints and the like in the use process and is not easy to clean. In order to improve the antifouling performance of ceramic tiles, the following two methods are generally adopted at present. Firstly, the vitrification degree of the ceramic tile is improved and the water absorption is reduced by changing the material composition of the ceramic tile or coating a layer of compact material on the surface of the ceramic tile before sintering; secondly, the ceramic anti-fouling liquid is coated after the ceramic tile is polished.
The ceramic polishing solution can form a layer of adsorption on the surface of the ceramic tile, and the ceramic tile has antifouling capacity due to the hydrophobic property of the membrane. The conventional polishing solution is mainly silica sol, however, the expansion and shrinkage performances of the main component of silica in the silica sol at high and low temperatures are not consistent with those of the ceramic tile surface, so that the ceramic tile is easy to crack in the water cooling process after polishing treatment, and the yield of the product is affected. Even if the qualified product is easy to crack due to the change of the environmental temperature during use.
Disclosure of Invention
In order to solve the technical problems, the first aspect of the invention provides an efficient anti-cracking polishing solution, which is prepared from 10-30 parts by weight of silica sol, 0.5-2 parts by weight of an auxiliary agent, 0.1-3 parts by weight of a dispersing agent, 1-5 parts by weight of a super-elastic polymer and 60-80 parts by weight of water;
the preparation method of the super elastic polymer comprises the following steps:
(1) adding 3.0mmol of MDI and 0.8-2.0 mmol of polyol into 20ml of DMAc, then heating the system to 80 ℃ in the atmosphere of introducing nitrogen, and reacting for 2-4 hours to obtain an isocyanate-terminated intermediate A;
(2) then cooling the intermediate A to room temperature, dropwise adding ethylenediamine under stirring, raising the temperature of the system to 70 ℃, reacting for 4 hours, and evaporating and concentrating to obtain the super-elastic polymer.
In a preferred embodiment of the present invention, the polyol is polyether polyol and/or modified polyether polyol.
As a preferred embodiment of the present invention, the modified polyether polyol has the following structural formula:
wherein x + z is (5-12), and y is (8-12).
As a preferable technical scheme of the invention, the MDI is functional MDI after functionalization treatment, and the preparation method comprises the following steps:
adding 3.0mmol of MDI and 1.0-1.5 mmol of functional monomer into 20ml of DMAc, then heating the system to 60-70 ℃ in the atmosphere of introducing nitrogen, and reacting for 1-3 hours to obtain the functional MDI;
the functional monomer has a functionality of not less than 2.
As a preferred technical solution of the present invention, the functional monomer has the following structural formula:
wherein R is1Is an aliphatic alkyl chain or an aliphatic ester chain, R2One or more selected from hydroxyl, amino and sulfhydryl.
In a preferred embodiment of the present invention, R1 in the functional monomer structure has the following structure:
according to a preferable technical scheme of the invention, the molar ratio of the polyether polyol to the modified polyether polyol is (1-2.5): 1.
as a preferable technical scheme of the invention, the number average molecular weight of the polyether polyol is 1200-1800.
As a preferable technical scheme of the invention, the particle size of the silica sol is not higher than 30 nm; preferably not higher than 20 nm.
The second aspect of the present invention provides a method for using the above-mentioned efficient anti-cracking polishing solution, comprising the following steps:
firstly, polishing the surface of a polished brick smoothly, then spraying polishing solution on the surface of the polished brick, and repeatedly polishing at least twice by using a roller set with a brush; wherein the spraying amount per square meter is 20-40 g; the polishing time is 20-40 s.
Has the advantages that: compared with the conventional silica sol polishing solution, the polishing solution provided by the invention can obviously improve the adhesion and bonding strength of the polishing solution to the surface of a ceramic tile, and simultaneously, the cracking and wrinkling of an antifouling layer formed by the polishing solution on the surface of the ceramic tile under high-low temperature alternation can be obviously improved through the specific structure of the super-elastic polymer and the interaction between the super-elastic polymer and the silica sol, so that the antifouling layer still keeps good integrity and good glossiness of a coating layer in a severe environment. In addition, after the super-elastic polymer prepared from the specially compounded polyalcohol and the functionalized MDI is added into the polishing solution, the ceramic tile treated by the polishing solution has good slip-stopping performance.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
The first aspect of the invention provides an efficient anti-cracking polishing solution, which is prepared from the following raw materials, by weight, 10-30 parts of silica sol, 0.5-2 parts of an auxiliary agent, 0.1-3 parts of a dispersing agent, 1-5 parts of a super-elastic polymer and 60-80 parts of water;
the preparation method of the super elastic polymer comprises the following steps:
(1) adding 3.0mmol of MDI and 0.8-2.0 mmol of polyol into 20ml of DMAc, then heating the system to 80 ℃ in the atmosphere of introducing nitrogen, and reacting for 2-4 hours to obtain an isocyanate-terminated intermediate A;
(2) then cooling the intermediate A to room temperature, dropwise adding ethylenediamine under stirring, raising the temperature of the system to 70 ℃, reacting for 4 hours, and evaporating and concentrating to obtain the super-elastic polymer.
The DMI is 4,4' -diphenylmethane diisocyanate. The polyol used in the process of preparing the superelastic polymer in the present invention is not particularly limited, and various polyols known to those skilled in the art may be used, such as polyether polyol, polyester polyol, polycarbonate polyol, polyurethane polyol, epoxy polyol, vegetable oil polyol, polyolefin polyol, acrylic polyol, vinyl monomer-modified polyol, and the like.
Examples of the polyether polyol include polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene ether glycol (PTMEG), and the like.
Examples of the polyester polyol include polycondensates obtained by reacting the low-molecular-weight polyol (preferably, diol) with a polybasic acid under known conditions.
In some embodiments, the polyol is a polyether polyol and/or a modified polyether polyol.
Further, the polyether polyol has a number average molecular weight of 1200-1800.
Preferably, the polyether polyol has a number average molecular weight of 1800. The number average molecular weight as described herein is a measure of the relative molecular weight of the polymer and can be measured in a manner well known to those skilled in the art.
Preferably, the polyether polyol is polytetramethylene ether glycol (PTMEG).
In some embodiments, the modified polyether polyol has the following structural formula:
wherein x + z is (5-12), and y is (8-12).
The modified polyether polyol is prepared by ring-opening polymerization of an epoxy compound (e.g., ethylene oxide, tetrahydrofuran, caprolactone, etc.) with a polyether (e.g., PEG, PPG, PTMEG, etc.) as an initiator and an alkali hydroxide as a catalyst, and the specific preparation method and operation are not particularly limited and may be performed according to conventional procedures well known to those skilled in the art.
Furthermore, the number of (x + z) segments in the structure of the modified polyether polyol is 8, and the number of y segments in the structure of the modified polyether polyol is 10.
The applicant finds that the thermal expansion and cold contraction inconsistency between the surface of the ceramic tile and the polishing solution is easy to occur in the water cooling process after the ceramic tile is ground and polished by the polishing solution, so that the coating layer formed on the surface of the ceramic tile by the polishing solution is easy to expand and contract freely, and the comprehensive performance of the ceramic tile is influenced. The applicant finds that the crack and wrinkle of the antifouling layer formed by the polishing solution can be remarkably improved by adding a proper amount of the super-elastic polymer into the formula of the ceramic polishing solution. The applicant obtains an intermediate A by reacting MDI with a polyol, and the intermediate A is reacted with a chain extender ethylenediamine to obtain the super elastic polymer. The polyether polyol or modified polyether polyol is selected as the polyol, and due to the methylene ether chain segment contained in the structure of the polyol, the polyol has good flexibility, and is favorable for enabling the super-elastic polymer to deform after receiving external stress or stimulation, so that the super-elastic polymer responds to the external stimulation. And MDI and ethylenediamine form urethane bonds and a large number of rigid benzene rings can be orderly arranged and aggregated to form chain segment anchoring points, so that the superelastic polymer can be restored to the original shape after being deformed due to external stimulation. When the super-elastic polymer is added into polishing solution to polish the surface of a ceramic tile, the silica sol in the polishing solution is uniformly filled in gaps and uneven planes on the surface of the ceramic, and the super-elastic polymer is uniformly filled in the surfaces of silica sol particles and gaps of the particles under the interaction between the super-elastic polymer and the silica sol, so that the volume change degree of the silica sol after film formation is reduced, the volume change of the silica sol in a high-temperature and low-temperature environment is counteracted through the elastic deformation of the super-elastic polymer, and the antifouling layer still keeps good film formation integrity and good surface performance (such as good glossiness and the like) in the high-temperature and low-temperature environment.
In addition, the applicant unexpectedly found that when polyether polyol and modified polyether polyol are used as the polyol for forming soft segments of the super-elastic polymer, the prepared super-elastic polymer has optimal toughness and elasticity, and particularly when the modified polyether is caprolactone modified polyether polyol, the number of caprolactone chain segments (x + z) in the structure of the caprolactone modified polyether polyol is 8, and the number of tetrahydrofuran chain segments is 10, the interaction between the super-elastic polymer and silica sol particles in a polishing solution reaches an optimal balance, and the super-elastic polymer can reduce the free spalling of the silica sol to the maximum extent, so that the super-elastic polymer still keeps good integrity and keeps good glossiness at higher temperature and lower temperature.
In some embodiments, the MDI is a functionalized functional MDI, and the preparation method comprises the steps of:
adding 3.0mmol of MDI and 1.0-1.5 mmol of functional monomer into 20ml of DMAc, then heating the system to 60-70 ℃ in the atmosphere of introducing nitrogen, and reacting for 1-3 hours to obtain the functional MDI;
the functional monomer has a functionality of not less than 2.
Preferably, the functional monomer has a functionality of 2 to 3.
Further preferably, the functional monomer has a functionality of 3. The functionality is the number of moles of reactive groups capable of reacting with isocyanate per mole of compound structure. For example, ethylenediamine has a functionality of 2.
In some embodiments, the functional monomer has the following structural formula:
wherein R is1Is an aliphatic alkyl chain or an aliphatic ester chain, R2One or more selected from hydroxyl, amino and sulfhydryl.
In the process of completing the invention, the applicant finds that in the process of preparing the super-elastic polymer, after MDI is subjected to functionalization treatment before the intermediate A is prepared, the impact resistance of the obtained super-elastic polymer on a polishing solution coating film layer is obviously improved, and meanwhile, the adhesive force of the polishing solution on the surface of a ceramic tile can be obviously improved. In the invention, functional monomers with the functionality degree of more than 2 are adopted to modify MDI, so that a micro-crosslinking structure is formed among super-elastic polymer chain segments, thereby improving the elasticity of the polishing solution film layer and improving the shock resistance of the polishing solution film layer. In the course of accomplishing this happy operation, the applicant found that when the functional monomer having the above structural formula of symmetrical three-branched chain structure is used, the impact resistance of the polishing solution is remarkably improved, and the adhesion of the polishing solution to the ceramic tile surface is also remarkably improved. The functional monomer has a symmetrical three-branched-chain structure, the tail end of each branched chain has an active group, and the active group at the tail end of each branched chain reacts with MDI to regulate and control the reaction molar ratio between the functional monomer and the MDI, so that the isocyanate-terminated three-branched-chain structure functional MDI is obtained through reaction. When the functional MDI reacts with the compounded polyether polyol and the ethylenediamine, the obtained super-elastic polymer has a plurality of same or similar long-chain structures similar to a multi-arm compound, and each chain segment structure is the same as the chain segment structure, so that the chain segments can better penetrate into gaps on the surface of a ceramic tile while being filled on the surface of silica sol particles, and the binding force between the silica sol and the surface of the ceramic tile is further improved. In addition, the same long-chain section structures in the super-elastic polymer structure are filled outside the surfaces of the silica sol particles, and can be randomly inserted among a plurality of silica sol particles, so that the expansion and contraction of the silica sol particles can be kept consistent, and the reduction of antifouling performance caused by uneven deformation capacity is avoided.
In some embodiments, R1 in the functional monomer structure has the following structure:
further, the molar ratio of the polyether polyol to the modified polyether polyol is (1-2.5): 1.
further, the molar ratio of the polyether polyol to the modified polyether polyol is 1.8: 1.
the applicant finds that when R1 in the adopted functional monomers has the same polyester structure with three branched chains, the polishing solution is used for polishing the surface of a ceramic tile and then a high-low temperature cycle experiment is carried out, the integrity of a coating layer on the surface of the ceramic tile is further improved, the ceramic tile keeps very high glossiness after the high-low temperature cycle test, and particularly when the polyol in the raw material for preparing the super-elastic polymer is compounded by polyether polyol with the number average molecular weight of 1200-1800 and caprolactone modified polyether polyol, and the molar ratio of the polyether polyol to the caprolactone modified polyether polyol is (1-2.5): 1 hour, the high and low temperature cycle experiment result of the polished tile is optimal. The applicant speculates that the structure and the amount of the polyether polyol and the modified polyether polyol are regulated, under the synergistic effect of the compounded polyol and the functional MDI, the cohesive strength of the super-elastic polymer is improved, the difference between the cohesive energy density of a urethane bond hard segment formed by the reaction of the MDI and the ethylenediamine in the super-elastic polymer structure and the cohesive energy density of a soft segment in the polyether structure is reduced, so that the larger volume change of the silica sol is reduced by smaller deformation of a polishing solution coating layer, and the polishing solution coating layer still keeps good surface performance and has high glossiness when placed at a lower temperature after being treated at a higher temperature. When R1 has the same polyester structure with three branched chains and the molar ratio of the polyhydric alcohol in the raw materials for preparing the super-elastic polymer reaches the compound ratio, the acting forces among the polyether chain segment, the polyester chain segment and the structures of the carbamic acid and the benzene ring reach a certain balance, so that the comprehensive performance of the polishing solution coating layer reaches the best.
In addition, the applicant also finds that the physical and chemical parameters of the silica sol in the polishing solution play a very critical role in the above performance of the polishing solution, and when the particle size of the silica sol is too large, the adhesion and the anti-cracking performance of the polishing solution to the surface of the ceramic tile are greatly influenced. Due to the same chain segment structures of the superelastic polymer, a plurality of three-dimensional network cavities are formed in the polishing solution in the polishing process of the surface of the ceramic tile, silica sol is uniformly dispersed in the cavities, and when the particle size of the silica sol is too large, the silica sol cannot be coated in the cavities formed by the superelastic polymer or the cavity structures are damaged, so that the interaction between the superelastic polymer and the silica sol is influenced.
The silica sol is a dispersion liquid of nano-scale silica particles in water or a solvent, and the colloidal particles are fine and have strong penetrability on a base material, can permeate into a base layer through capillaries and completely seal pores, and the surfaces of the colloidal particles have more uncondensed hydroxyl groups which are combined with a substrate, hydroxyl groups and hydroxyl groups, and hydroxyl groups and Si-H groups, so that a hydrophobic and oleophobic protective layer with special protective function and stable structure is formed on the surface of the base material.
In some embodiments, the silica sol has a particle size of no greater than 30 nm.
Further, the particle size of the silica sol is not more than 20 nm.
Further, the particle size of the silica sol is not more than 10-20 nm.
The silica sol particle size in the present invention refers to the average particle size in the silica sol, and can be obtained by testing according to methods known to those skilled in the art, such as scanning electron microscopy. The silica sol of the present invention can be commercially available, for example, HS-1430 available from Whiter nanotechnology Co., Ltd, Guangdong (average particle diameter of the silica sol is 10 to 20 nm; viscosity (25 ℃ C., mms 2/s): 6.5 or less; pH (25 ℃ C.): 9.0 to 10.5). The viscosity in the present invention refers to kinematic viscosity, and can be measured by a method known to those skilled in the art, and the viscosity in the present invention is measured by an NDJ-79 type viscometer.
The applicant unexpectedly discovers that when the super-elastic polymer prepared by adopting the specially compounded polyalcohol and the functionalized MDI is applied to the polishing solution, the ceramic tile treated by the polishing solution has good slip-stopping performance. The applicant speculates that the prepared super-elastic polymer has good structures and proportions of hard segments and soft segments, and has a specific structure with a plurality of same segments, so that a coating layer formed by the polishing solution has good thixotropic property. When the surface of the ceramic tile is subjected to external stress, the thixotropic property of the ceramic tile increases the friction force of the surface of the ceramic tile, so that the ceramic tile has a certain anti-slip effect.
The dispersing agent is a component of the polishing solution with high stability, wherein the dispersing agent is a silicon sol, a super elastic polymer, an auxiliary agent and the like, and the component is fully dispersed in the system, and the specific component is a surfactant. The dispersant of the present invention may be any dispersant known to those skilled in the art, such as nonionic surfactant, cationic surfactant, anionic surfactant, complex surfactant, etc. Examples include, but are not limited to, BYK-190 and the like.
Under the premise of not obviously reducing the comprehensive performance of the antifouling liquid, various additives well known by the technical personnel in the field can be selected, the selection of the types of the additives is not specially limited, and for example, a slippery feel enhancer, a penetration feel enhancer, a chelating agent, a stabilizer, a luminosity enhancer and the like can be selected.
The second aspect of the present invention provides a method for using the above-mentioned efficient anti-cracking polishing solution, comprising the following steps:
firstly, polishing the surface of a polished brick smoothly, then spraying polishing solution on the surface of the polished brick, and repeatedly polishing at least twice by using a roller set with a brush; wherein the spraying amount per square meter is 20-40 g; the polishing time is 20-40 s.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention. In addition, if not otherwise stated, the raw materials are all commercially available, wherein the auxiliary agent is a luminosity enhancer and is purchased from chemical industries, Inc. of New four seas, Hubei; the dispersant is BYK-190.
Examples
Example 1: the preparation raw materials of the efficient anti-cracking polishing solution comprise 22 parts by weight of silica sol, 0.8 part by weight of auxiliary agent, 1.7 parts by weight of dispersing agent, 4 parts by weight of super-elastic polymer and 75 parts by weight of water.
The silica sol is HS-1430 of Guangdong Whitner nano technology limited; the preparation method of the super elastic polymer comprises the following steps:
(1) adding 3.0mmol of MDI and 1.0mmol of functional monomer into 20ml of DMAc, then raising the temperature of the system to 65 ℃ under the atmosphere of introducing nitrogen, and reacting for 2 hours to obtain an isocyanate-terminated intermediate B;
(2) adding 1.0mmol of polyol into the intermediate B, then raising the temperature of the system to 80 ℃ in the atmosphere of introducing nitrogen, and reacting for 4 hours to obtain an isocyanate-terminated intermediate A;
(3) and then cooling the system of the intermediate A to room temperature, dropwise adding 0.55mmol of ethylenediamine under stirring, raising the temperature of the system to 70 ℃, reacting for 4 hours, evaporating, concentrating and drying to obtain the super-elastic polymer.
Wherein the polyols are polyether polyol and modified polyether polyol, and the molar ratio of the polyols is 1.8: 1.
the polyether polyol is polytetramethylene ether glycol (PTMEG) with the number average molecular weight of 1800. The modified polyether polyol has the following structural formula:
The functional monomer has the following structural formula:
Example 2: the preparation raw materials of the efficient anti-cracking polishing solution comprise 22 parts by weight of silica sol, 0.8 part by weight of auxiliary agent, 1.7 parts by weight of dispersing agent, 4 parts by weight of super-elastic polymer and 75 parts by weight of water.
The silica sol is HSD (the average particle size is 30-120 nm) of Guangdong Whitner nano technology limited company; the preparation method of the super elastic polymer comprises the following steps:
(1) adding 3.0mmol of MDI and 1.0mmol of functional monomer into 20ml of DMAc, then raising the temperature of the system to 65 ℃ under the atmosphere of introducing nitrogen, and reacting for 2 hours to obtain an isocyanate-terminated intermediate B;
(2) adding 1.0mmol of polyol into the intermediate B, then raising the temperature of the system to 80 ℃ in the atmosphere of introducing nitrogen, and reacting for 4 hours to obtain an isocyanate-terminated intermediate A;
(3) and then cooling the system of the intermediate A to room temperature, dropwise adding 0.55mmol of ethylenediamine under stirring, raising the temperature of the system to 70 ℃, reacting for 4 hours, evaporating, concentrating and drying to obtain the super-elastic polymer.
Wherein the polyols are polyether polyol and modified polyether polyol, and the molar ratio of the polyols is 1.8: 1.
the polyether polyol is polytetramethylene ether glycol (PTMEG) with the number average molecular weight of 1800. The modified polyether polyol has the following structural formula:
The functional monomer has the following structural formula:
Example 3: the preparation raw materials of the efficient anti-cracking polishing solution comprise 22 parts by weight of silica sol, 0.8 part by weight of auxiliary agent, 1.7 parts by weight of dispersing agent, 4 parts by weight of super-elastic polymer and 75 parts by weight of water.
The silica sol is HS-1430 of Guangdong Whitner nano technology limited; the preparation method of the super elastic polymer comprises the following steps:
(1) adding 1.5mmol of MDI and 1.0mmol of polyol into 20ml of DMAc, then raising the temperature of the system to 80 ℃ under the atmosphere of introducing nitrogen, and reacting for 4 hours to obtain an isocyanate-terminated intermediate A;
(2) and then cooling the system of the intermediate A to room temperature, dropwise adding 0.55mmol of ethylenediamine under stirring, raising the temperature of the system to 70 ℃, reacting for 4 hours, evaporating, concentrating and drying to obtain the super-elastic polymer.
Wherein the polyols are polyether polyol and modified polyether polyol, and the molar ratio of the polyols is 1.8: 1.
the polyether polyol is polytetramethylene ether glycol (PTMEG) with the number average molecular weight of 1800. The modified polyether polyol has the following structural formula:
Example 4: the preparation raw materials of the efficient anti-cracking polishing solution comprise 22 parts by weight of silica sol, 0.8 part by weight of auxiliary agent, 1.7 parts by weight of dispersing agent, 4 parts by weight of super-elastic polymer and 75 parts by weight of water.
The silica sol is HS-1430 of Guangdong Whitner nano technology limited; the preparation method of the super elastic polymer comprises the following steps:
(1) adding 3.0mmol of MDI and 1.0mmol of functional monomer into 20ml of DMAc, then raising the temperature of the system to 65 ℃ under the atmosphere of introducing nitrogen, and reacting for 2 hours to obtain an isocyanate-terminated intermediate B;
(2) adding 1.0mmol of polyol into the intermediate B, then raising the temperature of the system to 80 ℃ in the atmosphere of introducing nitrogen, and reacting for 4 hours to obtain an isocyanate-terminated intermediate A;
(3) and then cooling the system of the intermediate A to room temperature, dropwise adding 0.55mmol of ethylenediamine under stirring, raising the temperature of the system to 70 ℃, reacting for 4 hours, evaporating, concentrating and drying to obtain the super-elastic polymer.
Wherein the polyol is polytetramethylene ether glycol (PTMEG) having a number average molecular weight of 1800.
The functional monomer has the following structural formula:
Example 5: the preparation raw materials of the efficient anti-cracking polishing solution comprise 22 parts by weight of silica sol, 0.8 part by weight of auxiliary agent, 1.7 parts by weight of dispersing agent, 4 parts by weight of super-elastic polymer and 75 parts by weight of water.
The silica sol is HS-1430 of Guangdong Whitner nano technology limited; the preparation method of the super elastic polymer comprises the following steps:
(1) adding 3.0mmol of MDI and 1.0mmol of functional monomer into 20ml of DMAc, then raising the temperature of the system to 65 ℃ under the atmosphere of introducing nitrogen, and reacting for 2 hours to obtain an isocyanate-terminated intermediate B;
(2) adding 1.0mmol of polyol into the intermediate B, then raising the temperature of the system to 80 ℃ in the atmosphere of introducing nitrogen, and reacting for 4 hours to obtain an isocyanate-terminated intermediate A;
(3) and then cooling the system of the intermediate A to room temperature, dropwise adding 0.55mmol of ethylenediamine under stirring, raising the temperature of the system to 70 ℃, reacting for 4 hours, evaporating, concentrating and drying to obtain the super-elastic polymer.
Wherein the polyol is a modified polyether polyol having the following structural formula:
The functional monomer has the following structural formula:
Example 6: the preparation raw materials of the efficient anti-cracking polishing solution comprise 22 parts by weight of silica sol, 0.8 part by weight of auxiliary agent, 1.7 parts by weight of dispersing agent, 4 parts by weight of super-elastic polymer and 75 parts by weight of water.
The silica sol is HS-1430 of Guangdong Whitner nano technology limited; the preparation method of the super elastic polymer comprises the following steps:
(1) adding 3.0mmol of MDI and 1.0mmol of functional monomer into 20ml of DMAc, then raising the temperature of the system to 65 ℃ under the atmosphere of introducing nitrogen, and reacting for 2 hours to obtain an isocyanate-terminated intermediate B;
(2) adding 1.0mmol of polyol into the intermediate B, then raising the temperature of the system to 80 ℃ in the atmosphere of introducing nitrogen, and reacting for 4 hours to obtain an isocyanate-terminated intermediate A;
(3) then cooling the system of the intermediate A to room temperature, dropwise adding 0.55mmol of propylene glycol under stirring, raising the temperature of the system to 70 ℃, reacting for 4 hours, evaporating, concentrating and drying to obtain the super-elastic polymer.
Wherein the polyols are polyether polyol and modified polyether polyol, and the molar ratio of the polyols is 1.8: 1.
the polyether polyol is polytetramethylene ether glycol (PTMEG) with the number average molecular weight of 1800. The modified polyether polyol has the following structural formula:
The functional monomer has the following structural formula:
Example 7: the preparation raw materials of the efficient anti-cracking polishing solution comprise 22 parts by weight of silica sol, 0.8 part by weight of auxiliary agent, 1.7 parts by weight of dispersing agent, 4 parts by weight of super-elastic polymer and 75 parts by weight of water.
The silica sol is HS-1430 of Guangdong Whitner nano technology limited; the preparation method of the super elastic polymer comprises the following steps:
(1) adding 3.0mmol of MDI and 1.0mmol of functional monomer into 20ml of DMAc, then raising the temperature of the system to 65 ℃ under the atmosphere of introducing nitrogen, and reacting for 2 hours to obtain an isocyanate-terminated intermediate B;
(2) adding 1.0mmol of polyol into the intermediate B, then raising the temperature of the system to 80 ℃ in the atmosphere of introducing nitrogen, and reacting for 4 hours to obtain an isocyanate-terminated intermediate A;
(3) and then cooling the system of the intermediate A to room temperature, dropwise adding 0.55mmol of ethylenediamine under stirring, raising the temperature of the system to 70 ℃, reacting for 4 hours, evaporating, concentrating and drying to obtain the super-elastic polymer.
Wherein the polyols are polyether polyol and modified polyether polyol, and the molar ratio of the polyols is 1.8: 1.
the polyether polyol is polytetramethylene ether glycol (PTMEG) with the number average molecular weight of 1800. The modified polyether polyol has the following structural formula:
The functional monomer is butanediol-bis (mercaptopropionate) and has the following structure:
example 8: the preparation raw materials of the efficient anti-cracking polishing solution comprise 22 parts by weight of silica sol, 0.8 part by weight of auxiliary agent, 1.7 parts by weight of dispersing agent, 4 parts by weight of super-elastic polymer and 75 parts by weight of water.
The silica sol is HS-1430 of Guangdong Whitner nano technology limited; the preparation method of the super elastic polymer comprises the following steps:
(1) adding 3.0mmol of MDI and 1.0mmol of functional monomer into 20ml of DMAc, then raising the temperature of the system to 65 ℃ under the atmosphere of introducing nitrogen, and reacting for 2 hours to obtain an isocyanate-terminated intermediate B;
(2) adding 1.0mmol of polyol into the intermediate B, then raising the temperature of the system to 80 ℃ in the atmosphere of introducing nitrogen, and reacting for 4 hours to obtain an isocyanate-terminated intermediate A;
(3) and then cooling the system of the intermediate A to room temperature, dropwise adding 0.55mmol of ethylenediamine under stirring, raising the temperature of the system to 70 ℃, reacting for 4 hours, evaporating, concentrating and drying to obtain the super-elastic polymer.
Wherein the polyols are polyether polyol and modified polyether polyol, and the molar ratio of the polyols is 1.8: 1.
the polyether polyol is polytetramethylene ether glycol (PTMEG) with the number average molecular weight of 1800. The modified polyether polyol has the following structural formula:
The functional monomer is diethanolamine-tris (mercaptopropionate) and has the following structural formula:
example 9: the preparation raw materials of the efficient anti-cracking polishing solution comprise 22 parts by weight of silica sol, 0.8 part by weight of auxiliary agent, 1.7 parts by weight of dispersing agent, 16 parts by weight of super-elastic polymer and 75 parts by weight of water.
The silica sol is HS-1430 of Guangdong Whitner nano technology limited; the preparation method of the super elastic polymer comprises the following steps:
(1) adding 3.0mmol of MDI and 1.0mmol of functional monomer into 20ml of DMAc, then raising the temperature of the system to 65 ℃ under the atmosphere of introducing nitrogen, and reacting for 2 hours to obtain an isocyanate-terminated intermediate B;
(2) adding 1.0mmol of polyol into the intermediate B, then raising the temperature of the system to 80 ℃ in the atmosphere of introducing nitrogen, and reacting for 4 hours to obtain an isocyanate-terminated intermediate A;
(3) and then cooling the system of the intermediate A to room temperature, dropwise adding 0.55mmol of ethylenediamine under stirring, raising the temperature of the system to 70 ℃, reacting for 4 hours, evaporating, concentrating and drying to obtain the super-elastic polymer.
Wherein the polyols are polyether polyol and modified polyether polyol, and the molar ratio of the polyols is 1.8: 1.
the polyether polyol is polytetramethylene ether glycol (PTMEG) with the number average molecular weight of 1800. The modified polyether polyol has the following structural formula:
The functional monomer has the following structural formula:
Example 10: the preparation raw materials of the efficient anti-cracking polishing solution comprise 22 parts by weight of silica sol, 0.8 part by weight of auxiliary agent, 1.7 parts by weight of dispersing agent, 4 parts by weight of super-elastic polymer and 75 parts by weight of water.
The silica sol is HS-1430 of Guangdong Whitner nano technology limited; the preparation method of the super elastic polymer comprises the following steps:
(1) adding 3.0mmol of MDI and 1.0mmol of functional monomer into 20ml of DMAc, then raising the temperature of the system to 65 ℃ under the atmosphere of introducing nitrogen, and reacting for 2 hours to obtain an isocyanate-terminated intermediate B;
(2) adding 1.0mmol of polyol into the intermediate B, then raising the temperature of the system to 80 ℃ in the atmosphere of introducing nitrogen, and reacting for 4 hours to obtain an isocyanate-terminated intermediate A;
(3) and then cooling the system of the intermediate A to room temperature, dropwise adding 0.55mmol of ethylenediamine under stirring, raising the temperature of the system to 70 ℃, reacting for 4 hours, evaporating, concentrating and drying to obtain the super-elastic polymer.
Wherein the polyols are polyether polyol and modified polyether polyol, and the molar ratio of the polyols is 2.5: 1.
the polyether polyol is polytetramethylene ether glycol (PTMEG) with the number average molecular weight of 1800. The modified polyether polyol has the following structural formula:
The functional monomer has the following structural formula:
Example 11: the preparation raw materials of the efficient anti-cracking polishing solution comprise 22 parts by weight of silica sol, 0.8 part by weight of auxiliary agent, 1.7 parts by weight of dispersing agent, 4 parts by weight of super-elastic polymer and 75 parts by weight of water.
The silica sol is HS-1430 of Guangdong Whitner nano technology limited; the preparation method of the super elastic polymer comprises the following steps:
(1) adding 3.0mmol of MDI and 1.0mmol of functional monomer into 20ml of DMAc, then raising the temperature of the system to 65 ℃ under the atmosphere of introducing nitrogen, and reacting for 2 hours to obtain an isocyanate-terminated intermediate B;
(2) adding 1.0mmol of polyol into the intermediate B, then raising the temperature of the system to 80 ℃ in the atmosphere of introducing nitrogen, and reacting for 4 hours to obtain an isocyanate-terminated intermediate A;
(3) and then cooling the system of the intermediate A to room temperature, dropwise adding 0.55mmol of ethylenediamine under stirring, raising the temperature of the system to 70 ℃, reacting for 4 hours, evaporating, concentrating and drying to obtain the super-elastic polymer.
Wherein the polyols are polyether polyol and modified polyether polyol, and the molar ratio of the polyols is 1.8: 1.
the polyether polyol was polytetramethylene ether glycol (PTMEG), which had a number average molecular weight of 4500. The modified polyether polyol has the following structural formula:
The functional monomer has the following structural formula:
Example 12: the preparation raw materials comprise 22 parts by weight of silica sol, 0.8 part by weight of auxiliary agent, 1.7 parts by weight of dispersing agent and 75 parts by weight of water; the silica sol is HS-1430 of Whitler nanotechnology, Inc., Guangdong.
Performance testing
According to the using method of the polishing solution, the surface of a polished tile is polished smoothly, then the polishing solution prepared in the embodiment is sprayed on the surface of the polished tile and is repeatedly polished for three times by using a roller set with a brush, wherein the spraying amount per square meter is 40g, and the polishing time is 30s, and then the obtained sample is subjected to corresponding test.
1. According to the requirements of the national standard GB/T1720-89, the adhesion force tests of the polished brick surface polished by the antifouling liquid in the embodiment are respectively recorded as 1-7 grades, wherein the adhesion force of 7 grades is the worst, the adhesion force of 1 grade is the best, and the test results are shown in Table 1.
2. The peel strength (unit: N/25mm) of the polished tile surface polished with the antifouling liquid in the above examples was measured in accordance with the requirements of the national standard GB/T2792-1981 (polished tile as substrate), and the results are shown in Table 1.
3. The samples are subjected to an anti-skid performance test according to the standard of GB/T35153-2017, and the static friction coefficient of the samples in a wet state is tested.
4. Polishing the polished brick by using the anti-fouling liquid sample in the embodiment according to a specific use method, then placing the polished brick in an oven, heating to 70 ℃, keeping for 1 hour, taking out, placing in a-15 ℃ freezing device, keeping for 1 hour, and performing 3 times and 30 times of circulation to obtain a test sample. The polished tile surface was then tested using a gloss tester and the results were averaged (in GU units).
5. The samples used in the above examples were tested for impact resistance at-5 ℃ as required by the national standard GB/T1732-1993.
TABLE 1
TABLE 2
| Cycle 3 times gloss (degree) | Circulation 30 times gloss (degree) | Impact strength | |
| Example 1 | 101.8 | 100.3 | 45cm |
| Example 2 | 97.9 | 90.0 | 30cm |
| Example 3 | 91.4 | 82.5 | 30cm |
| Example 4 | 96.8 | 90.2 | 45cm |
| Example 5 | 97.5 | 90.9 | 35cm |
| Example 6 | 98.6 | 89.5 | 45cm |
| Example 7 | 92.4 | 84.0 | 40cm |
| Example 8 | 95.5 | 86.3 | 40cm |
| Example 9 | 101.2 | 100.5 | 45cm |
| Example 10 | 100.1 | 99.8 | 45cm |
| Example 11 | 98.0 | 96.5 | 45cm |
| Example 12 | 88.5 | 77.1 | 25cm |
As can be seen from the table, the polishing solution disclosed by the invention can have good adhesive force on the surface of a ceramic tile, can still keep good integrity of a coating layer in high-temperature and low-temperature environments, cannot cause the problems of cracking or wrinkling and the like, and still keeps good glossiness. In addition, by incorporating specific superelastic polymers, good impact properties at very low temperatures can be achieved.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. The efficient anti-cracking polishing solution is characterized by comprising the following raw materials, by weight, 10-30 parts of silica sol, 0.5-2 parts of an auxiliary agent, 0.1-3 parts of a dispersing agent, 1-5 parts of a super-elastic polymer and 60-80 parts of water;
the preparation method of the super elastic polymer comprises the following steps:
(1) adding 3.0mmol of MDI and 0.8-2.0 mmol of polyol into 20ml of DMAc, then heating the system to 80 ℃ in the atmosphere of introducing nitrogen, and reacting for 2-4 hours to obtain an isocyanate-terminated intermediate A;
(2) then cooling the intermediate A to room temperature, dropwise adding ethylenediamine under stirring, raising the temperature of the system to 70 ℃, reacting for 4 hours, and evaporating and concentrating to obtain the super-elastic polymer.
2. The efficient anti-cracking polishing solution according to claim 1, wherein the polyol is polyether polyol and/or modified polyether polyol.
3. The efficient anti-cracking polishing solution according to claim 2, wherein the modified polyether polyol has the following structural formula:
wherein x + z is (5-12), and y is (8-12).
4. The efficient anti-cracking polishing solution according to claim 2, wherein the MDI is a functionalized functional MDI, and the preparation method comprises the following steps:
adding 3.0mmol of MDI and 1.0-1.5 mmol of functional monomer into 20ml of DMAc, then heating the system to 60-70 ℃ in the atmosphere of introducing nitrogen, and reacting for 1-3 hours to obtain the functional MDI;
the functional monomer has a functionality of not less than 2.
5. The efficient anti-cracking polishing solution according to claim 4, wherein the functional monomer has the following structural formula:
wherein R is1Is an aliphatic alkyl chain or an aliphatic ester chain, R2One or more selected from hydroxyl, amino and sulfhydryl.
6. The efficient anti-cracking polishing solution according to claim 5, wherein R1 in the functional monomer structure has the following structure:
7. the efficient anti-cracking polishing solution according to claim 5, wherein the molar ratio of the polyether polyol to the modified polyether polyol is (1-2.5): 1.
8. the efficient anti-cracking polishing solution according to claim 7, wherein the polyether polyol has a number average molecular weight of 1200 to 1800.
9. The efficient anti-cracking polishing solution according to any one of claims 1 to 8, wherein the particle size of the silica sol is not more than 30 nm; preferably not higher than 20 nm.
10. The use method of the efficient anti-cracking polishing solution according to any one of claims 1 to 9, characterized by comprising the following steps:
firstly, polishing the surface of a polished brick smoothly, then spraying polishing solution on the surface of the polished brick, and repeatedly polishing at least twice by using a roller set with a brush; wherein the spraying amount per square meter is 20-40 g; the polishing time is 20-40 s.
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| CN111004575A (en) * | 2019-12-19 | 2020-04-14 | 清远市宏图助剂有限公司 | Durable antifouling liquid and preparation method thereof |
| CN111073519A (en) * | 2019-12-19 | 2020-04-28 | 清远市宏图助剂有限公司 | Core-shell structure ceramic polishing solution |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116731578A (en) * | 2023-06-07 | 2023-09-12 | 佛山市安塔邦新材料有限公司 | Hard crystal face wear-resistant anti-slip agent |
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