CN110591432A - Self-flame-retardant antibacterial multifunctional water-based paint and preparation method thereof - Google Patents
Self-flame-retardant antibacterial multifunctional water-based paint and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/00—Properties
- C08L2201/04—Antistatic
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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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Abstract
The invention relates to a self-flame-retardant antibacterial multifunctional water-based paint and a preparation method thereof, wherein the paint comprises the following components in parts by weight: 100.0-150.0 parts of self-flame-retardant antibacterial waterborne polyester resin, 30.0-50.0 parts of graphene modified waterborne polyester resin, 4.0-8.0 parts of coupling agent, 2.0-20.0 parts of spherical silica powder, 1.0-8.0 parts of white carbon black, 1.0-10.0 parts of barium sulfate, 0-18.0 parts of nano color paste, 8.0-18.0 parts of auxiliary agent and 10.0-40.0 parts of deionized water; the graphene modified waterborne polyester resin is prepared by reacting organic acid anhydride, special graphene, lauric acid monoglyceride, oligomer dihydric alcohol, polyol, 2-bipyridyl-5-carboxylic acid, dimethylolpropionic acid and a neutralizing agent; the self-flame-retardant antibacterial water-based polyester resin is mainly prepared from organic acid anhydride, carboxylic acid Schiff base, polybasic acid, polyalcohol, 2-chloro-5-bromobenzoic acid, dimethylolpropionic acid and a neutralizer; the self-flame-retardant antibacterial multifunctional water-based paint prepared by the invention does not need a flame retardant and an antibacterial agent, and has a lasting flame-retardant antibacterial effect.
Description
Technical Field
The invention relates to a multifunctional water-based paint, in particular to a self-flame-retardant antibacterial multifunctional water-based paint and a preparation method thereof, belonging to the technical field of water-based functional paints.
Background
In various fields, the paint is widely applied, and along with the attention of people on health, the functionalization and environmental protection of the paint are gradually accepted by the market. A large amount of bacteria and virus microorganisms exist in the environment, which not only can affect the health of people, but also can greatly affect the quality of a coating film formed by the coating.
The existing commercial antibacterial coating adopts antibacterial metal ions (silver ions, copper ions and the like) to exchange and adsorb on a porous carrier, the antibacterial metal ions are added into the coating as an antibacterial component and slowly permeate out from a pore channel through the metal ions, when bacteria contact a plate surface, negatively charged bacterial cells can attract the metal ions to enter cell bodies and are tightly combined with negatively charged chemical substances in a system, the biological electrical balance of the system is destroyed when the bacteria replicate, and simultaneously, the protein of the bacterial bodies is denatured to destroy the propagation and kill the bacteria. However, the antibacterial product has the defects of low adsorption rate, effective metal adsorption rate below 5 percent and poor sterilization effect.
Chinese patent CN107987593A discloses an antibacterial polyester resin varnish, belonging to the technical field of paint production. The antibacterial polyester resin varnish is prepared from the following raw materials in parts by mass: 20-30 parts of phthalic anhydride, 40-65 parts of phthalic anhydride, 8-20 parts of 1, 2-propylene glycol, 3-12 parts of polyethylene glycol, 1-5 parts of organic tin catalyst, 60-110 parts of dimethylbenzene, 2-8 parts of lithium carbonate, 8-15 parts of nano titanium dioxide, 9-18 parts of dipentene, 2-7 parts of isothiazolinone, 1-5 parts of nano silver powder and 1-3 parts of silane coupling agent. The polyester resin varnish disclosed by the invention is added with lithium carbonate, isothiazolinone, nano silver powder and other components.
Chinese patent CN109181448A discloses an antibacterial and bactericidal latex paint which comprises the following components in parts by weight: 30-50 parts of acrylic emulsion, 10-20 parts of polyester resin, 5-15 parts of coconut diethanolamide, 5-10 parts of calcium fluoride, 1-3 parts of trimethylamine hydrochloride, 1-5 parts of titanium dioxide, 5-10 parts of bentonite, 3-8 parts of an inorganic antibacterial agent and 100-200 parts of deionized water; the emulsion paint is non-toxic and odorless, does not contain volatile organic matters which cause harm to human health and environment, has good leveling property and stable quality, has the functions of antibiosis and sterilization, and does not change color or fall off after being used for a long time.
On the other hand, along with the improvement of living standard of people, flame-retardant architectural coatings and flame-retardant finish coatings are popular with consumers. Chinese patent CN103773185A discloses a preparation method of a flame-retardant unsaturated polyester resin coating, which comprises the following steps: (1) preparing flame-retardant unsaturated polyester resin (2), adding 100 parts of flame-retardant unsaturated polyester resin into an enamel stirring cylinder, simultaneously adding 20-25 parts of petroleum ether and 35-50 parts of organic solvent, and stirring at high speed for 10-15 minutes; (3) uniformly mixing 5-8 parts of pigment and 12-15 parts of extender pigment, slowly adding the mixture into an enamel stirring cylinder, adding the mixture of the pigment and the extender pigment while stirring, heating to 75 ℃, thermalizing for 1 hour, cooling and discharging to obtain the flame-retardant unsaturated polyester resin coating. The invention has the advantages of strong flexibility, good wettability, difficult yellowing, good gloss and color retention, high gloss, excessive baking resistance, simple material, low cost and easy processing and production. However, the flame-retardant organic silicon rubber does not contain antibacterial performance, the flame-retardant groups are easy to coat, contain more organic solvents, are not environment-friendly, and are difficult to meet the requirements of complex environments.
Therefore, the development of the environment-friendly water-based paint with the antibacterial and flame retardant functions meets the requirements of social development and has wide application prospect.
Disclosure of Invention
The invention introduces the water-based polyester resin with good flame retardance and antibacterial property as the main film forming substance of the coating, and the flame retardance and antibacterial groups of the self-flame-retardant antibacterial water-based polyester resin are positioned at two ends of the high polymer resin, so that the flame retardance and antibacterial property of the self-flame-retardant antibacterial water-based polyester resin can be fully exerted.
The self-flame-retardant antibacterial multifunctional water-based paint does not need a flame retardant and an antibacterial agent, and effectively solves the problems of uneven dispersion, easy sedimentation, non-lasting effect and the like of the flame retardant and the antibacterial agent in the paint.
In order to solve the problems of the multifunctional requirement, compatibility and the like of the coating, the graphene modified waterborne polyester resin and the coupling agent are added.
The invention aims to provide a self-flame-retardant antibacterial multifunctional water-based paint.
The invention also provides a preparation method of the self-flame-retardant antibacterial multifunctional water-based paint.
The invention relates to a self-flame-retardant antibacterial multifunctional water-based paint which comprises the following basic formula in parts by weight: 100.0-150.0 parts of self-flame-retardant antibacterial waterborne polyester resin, 30.0-50.0 parts of graphene modified waterborne polyester resin, 4.0-8.0 parts of coupling agent, 2.0-20.0 parts of spherical silicon micropowder, 1.0-8.0 parts of white carbon black, 1.0-10.0 parts of barium sulfate, 0-18.0 parts of nano color paste, 8.0-18.0 parts of auxiliary agent and 10.0-40.0 parts of deionized water.
The graphene modified waterborne polyester resin is prepared by reacting organic acid anhydride, special graphene, lauric acid monoglyceride, oligomer dihydric alcohol, polyol, 2-bipyridyl-5-carboxylic acid, dimethylolpropionic acid and a neutralizing agent.
The self-flame-retardant antibacterial water-based polyester resin comprises the following components in parts by weight: 6.0-12.0 parts of organic acid anhydride, 3.0-5.0 parts of carboxylic acid Schiff base, 3.0-8.0 parts of polybasic acid, 6.0-20.0 parts of polyhydric alcohol, 1.2-3.5 parts of 2-chloro-5-bromobenzoic acid, 1.5-3.5 parts of dimethylolpropionic acid, 2.0-5.0 parts of dimethylbenzene, 2.0-5.0 parts of neutralizing agent and 45.0-65.0 parts of deionized water.
The auxiliary agent is at least one of a wetting agent, a dispersing agent, a defoaming agent, a flatting agent, a thickening agent, a pH regulator, an antifreezing agent, a film-forming auxiliary agent and a nano auxiliary agent.
The coupling agent is one or the combination of two of silane coupling agent and borate coupling agent.
The invention relates to a preparation method of a self-flame-retardant antibacterial multifunctional water-based paint, which comprises the following preparation steps:
a. uniformly stirring the self-flame-retardant antibacterial waterborne polyester resin, the graphene modified waterborne polyester resin and the film-forming additive at normal temperature, standing for 8.0-12.0 h to allow the film-forming additive and the two waterborne resins to mutually permeate to obtain a film-forming mixture;
b. uniformly stirring a dispersing agent, a wetting agent, a multifunctional additive, a defoaming agent and deionized water at normal temperature, then adding spherical silicon micro powder, white carbon black and barium sulfate for high-speed dispersion, and then adding nano color paste for uniform stirring;
c. naturally cooling to room temperature, sequentially adding the film forming mixture, the flatting agent and the defoaming agent, uniformly stirring, adjusting the pH value to 7.5-8.0 by using the multifunctional auxiliary agent, diluting and adding the thickening agent and the deionized water according to the mass ratio of 1:10, and finally adding a proper amount of deionized water to adjust to the specified viscosity. Thus obtaining the self-flame-retardant antibacterial multifunctional water-based paint.
The self-flame-retardant antibacterial multifunctional water-based paint prepared by the invention has the following advantages:
1) the coating film has good leveling property in the film forming process, does not produce sagging, does not need an external flame retardant, and effectively overcomes the defects of uneven dispersion, easy precipitation, pulverization and the like of the external flame retardant.
2) The self-flame-retardant antibacterial multifunctional water-based paint prepared by the invention does not need to be additionally added with an antibacterial agent, effectively solves the problem of influence of the externally added antibacterial agent on the performance of a paint film, and has non-lasting antibacterial performance.
3) The self-flame-retardant antibacterial multifunctional water-based paint prepared by the invention is environment-friendly and has the multifunctional characteristics of good adhesive force, fullness, durability, chemical resistance, antistatic performance and the like; can be used for protecting and decorating various surfaces of woodware, steel structures, concrete, electronic product shells and the like.
Detailed Description
The present invention is further described with reference to the following examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
Example 1
A self-flame-retardant antibacterial multifunctional water-based paint is prepared by the following preparation process:
a. uniformly stirring 120.0 parts of self-flame-retardant antibacterial waterborne polyester resin, 40.0 parts of graphene modified waterborne polyester resin and 10.0 parts of film-forming additive at normal temperature, standing for 12.0 hours to allow the film-forming additive and the two waterborne resins to mutually permeate to obtain a film-forming mixture;
b. uniformly stirring 0.8 part of dispersing agent, 0.4 part of wetting agent, 0.5 part of multifunctional assistant, 0.3 part of defoaming agent and 8.0 parts of deionized water at normal temperature, then adding 8.0 parts of spherical silicon powder, 4.0 parts of white carbon black and 6.0 parts of barium sulfate for high-speed dispersion, and then adding 8.0 parts of nano color paste and 5.0 parts of coupling agent for uniform stirring;
c. and naturally cooling to room temperature, sequentially adding the film forming mixture, 0.5 part of flatting agent and 0.2 part of defoaming agent, uniformly stirring, adjusting the pH value to 7.5-8.0 by using 0.4 part of multifunctional additive, diluting and adding 0.5 part of thickening agent and 5.0 parts of deionized water, finally adding 15.0 parts of deionized water, adjusting the viscosity to 25 ℃, coating in 4 cups, and stirring for 46 seconds for 26. Thus obtaining the self-flame-retardant antibacterial multifunctional water-based paint.
Example 2
A self-flame-retardant antibacterial multifunctional water-based paint is prepared by the following preparation process:
a. uniformly stirring 100.0 parts of self-flame-retardant antibacterial waterborne polyester resin, 50.0 parts of graphene modified waterborne polyester resin and 9.0 parts of film-forming additive at normal temperature, standing for 11.0 hours to allow the film-forming additive and the two waterborne resins to mutually permeate to obtain a film-forming mixture;
b. uniformly stirring 0.5 part of dispersing agent, 0.3 part of wetting agent, 0.4 part of multifunctional assistant, 0.3 part of defoaming agent and 5.0 parts of deionized water at normal temperature, then adding 4.0 parts of spherical silicon powder, 3.0 parts of white carbon black and 4.0 parts of barium sulfate for high-speed dispersion, and then adding 5.0 parts of nano color paste and 5.0 parts of coupling agent for uniform stirring;
c. and naturally cooling to room temperature, sequentially adding the film forming mixture, 0.5 part of flatting agent and 0.3 part of defoaming agent, uniformly stirring, adjusting the pH value to 7.5-8.0 by using 0.4 part of multifunctional additive, diluting and adding 0.4 part of thickening agent and 4.0 parts of deionized water, finally adding 13.0 parts of deionized water, adjusting the viscosity to 25 ℃, coating in 4 cups, and stirring for 46 seconds for 36. Thus obtaining the self-flame-retardant antibacterial multifunctional water-based paint.
Example 3
A self-flame-retardant antibacterial multifunctional water-based paint is prepared by the following preparation process:
a. uniformly stirring 140.0 parts of self-flame-retardant antibacterial waterborne polyester resin, 35.0 parts of graphene modified waterborne polyester resin and 11.0 parts of film-forming aid at normal temperature, standing for 12.0 hours to allow the film-forming aid and the two waterborne resins to mutually permeate to obtain a film-forming mixture;
b. uniformly stirring 0.8 part of dispersing agent, 0.4 part of wetting agent, 0.5 part of multifunctional assistant, 0.4 part of defoaming agent and 8.0 parts of deionized water at normal temperature, then adding 10.0 parts of spherical silicon powder, 4.0 parts of white carbon black and 8.0 parts of barium sulfate for high-speed dispersion, then adding 6.0 parts of nano color paste and 6.0 parts of coupling agent for uniform stirring; c. and naturally cooling to room temperature, sequentially adding the film forming mixture, 0.6 part of flatting agent and 0.3 part of defoaming agent, uniformly stirring, adjusting the pH value to 7.5-8.0 by using 0.6 part of multifunctional additive, diluting and adding 0.6 part of thickening agent and 6.0 parts of deionized water, finally adding 16.0 parts of deionized water, adjusting the viscosity, coating 4 cups at 25 ℃, and coating for 47 seconds for 56. Thus obtaining the self-flame-retardant antibacterial multifunctional water-based paint.
According to relevant standards, water resistance (GB/T1733-1993), adhesion (GB/T9286-1998), salt fog resistance (GB/T1771-2007), artificial aging resistance (GB/T14522), pencil hardness (GB/T6739-1996), acid resistance ((10% HCl) GB/T1763-1979), alkali resistance ((10% NaOH) GB/1763-1979), electromagnetic shielding (GB/T25471-2010) and the like, a self-flame-retardant antibacterial multifunctional water-based paint and a conventional water-based paint (a comparative example) are subjected to comparative performance index tests, and the test results are shown in Table 1:
table 1: technical index of contrast performance of coating
It can be seen from table 1 that the samples of examples 1,2 and 3 of the present invention have better fullness, electromagnetic shielding property, salt spray resistance, artificial aging resistance, alkali resistance, acid resistance and the like than the conventional water-based paint.
Comparing the performance of the embodiment of the invention with that of the existing antibacterial coating (comparative example), the antibacterial performance of the coating is tested according to the standard of HG/T3950-2007 antibacterial coating, and the test results are shown in the following table 2:
table 2: test results of antibacterial properties of the coating
It can be seen from table 2 that the antibacterial performance of the samples of examples 1,2 and 3 of the present invention is better than that of the existing antibacterial coating (comparative example).
After the samples of the self-flame-retardant antibacterial multifunctional water-based paint disclosed by the invention in the embodiments 1,2 and 3 are subjected to simulated natural aging for 2 years, the antibacterial performance of the coating is tested according to the standard of HG/T3950-2007 antibacterial paint, and the antibacterial performance is basically unchanged, because the antibacterial groups are bonded on the high-molecular resin structure in a chemical bond form, the coating is not easy to fall off, the antibacterial effect is lasting, and the defects that the antibacterial effect of an externally-added antibacterial agent is not lasting and the like are effectively overcome.
The performance of the embodiment of the invention is compared with that of the existing flame-retardant coating (comparative example), the flame-retardant performance is tested according to GB12441-2005, and the test results are shown in Table 3:
table 3: technical index of flame retardant property of coating
It can be seen from table 3 that the flame retardant properties of examples 1,2 and 3 of the present invention are better than those of the conventional flame retardant coating.
In the examples of the self-flame-retardant antibacterial multifunctional water-based paint, the content of the free flame-retardant monomer in the paint sample is detected by gas chromatography, and the test results are shown in table 4.
Table 4: free flame retardant monomer content in the examples
As shown in Table 4, the self-flame-retardant antibacterial multifunctional water-based paint provided by the invention has the advantages that the halogen-containing flame-retardant groups are fixed on the resin structure in a chemical bond mode, so that the paint is not easy to decompose and fall off, the paint can have lasting self-flame retardant property without adding other flame retardants, and the defects that the externally added flame retardants are easy to decompose, fall off, and are not uniformly dispersed are overcome.
Although the present invention has been described in detail and with reference to exemplary embodiments thereof, it will be apparent to one skilled in the art that various changes, modifications and variations can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (5)
1. A self-flame-retardant antibacterial multifunctional water-based paint is characterized in that: the self-flame-retardant antibacterial multifunctional water-based paint comprises the following basic formula in parts by weight: 100.0-150.0 parts of self-flame-retardant antibacterial waterborne polyester resin, 30.0-50.0 parts of graphene modified waterborne polyester resin, 4.0-8.0 parts of coupling agent, 2.0-20.0 parts of spherical silica powder, 1.0-8.0 parts of white carbon black, 1.0-10.0 parts of barium sulfate, 0-18.0 parts of nano color paste, 8.0-18.0 parts of auxiliary agent and 10.0-40.0 parts of deionized water;
the graphene modified waterborne polyester resin is prepared by reacting organic acid anhydride, special graphene, lauric acid monoglyceride, oligomer dihydric alcohol, polyhydric alcohol, 2-bipyridine-5-carboxylic acid, dimethylolpropionic acid and a neutralizing agent.
2. The self-flame-retardant antibacterial waterborne polyester resin as claimed in claim 1, which comprises the following components in parts by weight: 6.0-12.0 parts of organic acid anhydride, 3.0-5.0 parts of carboxylic acid Schiff base, 3.0-8.0 parts of polybasic acid, 6.0-20.0 parts of polyhydric alcohol, 1.2-3.5 parts of 2-chloro-5-bromobenzoic acid, 1.5-3.5 parts of dimethylolpropionic acid, 2.0-5.0 parts of dimethylbenzene, 2.0-5.0 parts of neutralizing agent and 45.0-65.0 parts of deionized water.
3. The self-flame-retardant antibacterial multifunctional water-based paint as claimed in claim 1, wherein: the auxiliary agent is at least one of a wetting agent, a dispersing agent, a defoaming agent, a flatting agent, a thickening agent, a pH regulator, an antifreezing agent, a film-forming auxiliary agent and a nano auxiliary agent.
4. The self-flame-retardant antibacterial multifunctional water-based paint as claimed in claim 1, wherein: the coupling agent is one or the combination of two of silane coupling agent and borate coupling agent.
5. The self-flame-retardant antibacterial multifunctional water-based paint as claimed in claim 1, wherein: the preparation method comprises the following preparation processes:
a. uniformly stirring the self-flame-retardant antibacterial waterborne polyester resin, the graphene modified waterborne polyester resin and the film-forming additive at normal temperature, standing for 8.0-12.0 h to allow the film-forming additive and the two waterborne resins to mutually permeate to obtain a film-forming mixture;
b. uniformly stirring a dispersing agent, a wetting agent, a multifunctional additive, a defoaming agent and deionized water at normal temperature, then adding spherical silicon micro powder, white carbon black and barium sulfate for high-speed dispersion, and then adding nano color paste for uniform stirring;
c. naturally cooling to room temperature, sequentially adding the film forming mixture, the flatting agent and the defoaming agent, uniformly stirring, adjusting the pH value to 7.5-8.0 by using a multifunctional auxiliary agent, diluting and adding the thickening agent and deionized water according to the mass ratio of 1:10, and finally adding a proper amount of deionized water, and adjusting to a specified viscosity; thus obtaining the self-flame-retardant antibacterial multifunctional water-based paint.
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| CN109554056A (en) * | 2018-10-16 | 2019-04-02 | 韶关市合众化工有限公司 | It is a kind of functional from anti-flaming dope |
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2019
- 2019-09-01 CN CN201910820186.8A patent/CN110591432A/en active Pending
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| US10066125B2 (en) * | 2015-10-28 | 2018-09-04 | Korea Institute Of Science And Technology | Lignin-containing coating composition and ultrafine fibers including the same |
| CN106633013A (en) * | 2016-12-30 | 2017-05-10 | 合众（佛山）化工有限公司 | Graphene modified aqueous silicone alkyd resin and preparation method thereof |
| CN107936819A (en) * | 2017-12-15 | 2018-04-20 | 合众（佛山）化工有限公司 | A kind of inflaming-retarding antifouling antibiotic water paint |
| CN109554056A (en) * | 2018-10-16 | 2019-04-02 | 韶关市合众化工有限公司 | It is a kind of functional from anti-flaming dope |
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