CN108912960A - A kind of selfreparing anticorrosive paint - Google Patents
A kind of selfreparing anticorrosive paint Download PDFInfo
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- CN108912960A CN108912960A CN201810749642.XA CN201810749642A CN108912960A CN 108912960 A CN108912960 A CN 108912960A CN 201810749642 A CN201810749642 A CN 201810749642A CN 108912960 A CN108912960 A CN 108912960A
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- self
- corrosion
- repair function
- anticorrosive paint
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Classifications
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/106—Anti-corrosive paints containing metal dust containing Zn
-
- 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
- C09D7/20—Diluents or solvents
-
- 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
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0893—Zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
Abstract
The present invention discloses a kind of selfreparing anticorrosive paint, anticorrosive paint uses the first and second bicomponent systems, wherein first component includes epoxy resin, self-repair function additive, corrosion-inhibitive pigments, filler, auxiliary agent and solvent, second group is divided into curing agent, self-repair function additive is complex microsphere, corrosion-inhibitive pigments are more than one zinc powder, auxiliary agent is BYK142, BYK320, filler is titanium dioxide, one or more mix in silica, mica powder, solvent refers to that butyl acetate, dimethylbenzene mix, and curing agent is 650 Versamids.The present invention can form in time new protective capability in breakage, can effectively solve the problems, such as that its protective performance is lost when conventional coating damage.
Description
Technical field
The present invention relates to marine anti corrosion technology fields, it particularly relates to a kind of selfreparing anticorrosive paint.
Background technique
Coating protection is at present to include the various equipment in fields such as aerospace, automobile manufacture, petroleum and petrochemical industry, facility using most
Extensive anticorrosion means.But as coating for, in use, inevitably because of the factors such as natural, artificial
It influences, causes it to occur cracking and damaged, limit by various conditions, people are difficult to find coating breakage in time and carry out to it
Repairing in time, when various corrosive mediums invade equipment, when being protected surface of facility by breakage, it is meant that the guarantor of coating
Shield effect is decreased or even thorough forfeiture, if such state is persistently spread, will be caused to equipment, facility further,
Bigger damage can even cause major accident sometimes.Solve the problems, such as that one of this approach is exactly to develop to be reviewed one's lessons by oneself
Multiple coating material.
Summary of the invention
The present invention relates to a kind of selfreparing anticorrosive paint and preparation method thereof, it can effectively solve the problem that and formed in time in breakage
New protective capability can effectively solve the technical issues of conventional coating protection performance is lost.
To achieve the above object, the technical scheme adopted by the invention is as follows：A kind of selfreparing anticorrosive paint, the anticorrosive paint
Using the first and second bicomponent systems, wherein first component includes epoxy resin, self-repair function additive, corrosion-inhibitive pigments, filler, helps
Agent and solvent, second group are divided into curing agent,
It is characterized in that：Wherein, the self-repair function additive is micron order complex microsphere, the shell of complex microsphere
It is silica, corrosion inhibiter is loaded in shell, corrosion inhibiter is benzo tetrazole or imidazoles beautiful jade or organozinc complex, and described is resistance to
Anticorrosion pigment is the zinc powder of two or more partial sizes, and the filler is titanium dioxide, silica, two or more mixed in mica powder
It closes, the auxiliary agent is BYK142 and/or BYK320, and the solvent is butyl acetate, dimethylbenzene mixes, described
Curing agent be polyamide 6 50；
The parts by weight of said components are respectively：It is 30-65 parts of epoxy resin, 5-30 parts of self-repair function additive, corrosion-resistant
15-80 parts of pigment, 10-40 parts of filler, 0.1-3 parts of wetting dispersing agent, 0.1-3 parts of levelling agent, 10-30 parts of solvent, curing agent 70-
80 parts, the first and second components are with hundred parts of ratios of weight by epoxide equivalent: amine hydrogen equivalent=0.9: 1 is used in mixed way.
Technical solution may further be：The epoxy resin is aliphatic epoxy resin.
Technical solution may further be：The shell of the self-repair function additive is silica or aluminium oxide, shell
Interior loading corrosion inhibiter material, corrosion inhibiter are benzo tetrazole or imidazoles beautiful jade or organozinc complex.
Technical solution may further be：Mixed solvent refer to 10-30 parts of butyl acetates and the mixing of 30-70 parts of dimethylbenzene and
At.
Wherein, the method for preparing self-repair function additive is：In dehydrated alcohol, hexadecyl trichlorosilane is instilled,
Ultrasonic agitation, stirring blade periphery linear velocity 1-2 meter per second are slowly added to ethyl orthosilicate, after ultrasonic agitation, outside stirring blade
1 meter per second of contour speed sequentially adds ammonium hydroxide and water and filters after reaction 7 hours, and washing, alcohol is washed, and 40 DEG C are dried in vacuo 5 hours
After obtain mesopore silica dioxide hollow sphere, which is distributed in the aqueous solution containing corrosion inhibiter and is stirred, stirring blade periphery
Linear velocity 3-5 meter per second, after dispersion 2 hours, after standing 12 hours, filtering obtains self-repair function additive after dry.
In conclusion beneficial effects of the present invention are：
1. introducing a kind of self-repair function additive in the design of unique anticorrosion paint formulation, it and corrosion-resistant face are utilized
The optimization collocation of material and filler and synergistic effect, are realized at coating damage (exposing metal ground), in external environment
Self-repair function additive can release a kind of liquid comprising sustained release agent under the stimulation of condition (moist, suitable pH value),
The ground metal surface exposed forms one layer of new protective film, the intrusion of corrosive medium is prevented, to form new guarantor in time
Shield ability can effectively solve the problems, such as that its protective performance is lost when conventional coating damage.
2. using the zinc powder of two or more different-grain diameter sizes as corrosion-inhibitive pigments, loading can controlled
Under the premise of, reach better conductive communication, obtains with self-repair function additive and preferably match and synergistic action effect；Choosing
With polyamide 6 50 or 650 epoxy curing agents, adhesive force, water resistance and flexible comprehensive performance are best, test
The solidification and anticorrosion endurance obtained afterwards is best.
3. BYK auxiliary agent after all previous test, summarizes the collaboration for finding itself and self-repair function additive, corrosion-inhibitive pigments
Act on best, optimum results are best；It is dosed while wetting dispersing agent and levelling agent, increases mixing between component and solvent
Property, interface strength is reduced, it is antistatic, improve mobility and wetability.
4. solvent is mixed using butyl acetate, dimethylbenzene, it can sufficiently adjust and the solubility and film of resin are waved
The result of hair property；When each component uses specific weight ratio, the first and second components of Summary introduction are with weight hundred
Part proportion when, especially when the first and second components with hundred parts of ratios of weight by epoxide equivalent: amine hydrogen equivalent=0.9: 1 is used in mixed way so that
Hardness, adhesive force and the flexible comprehensive performance of coating have reached optimum state.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below with reference to embodiment, the present invention is made
Further to be described in detail, exemplary embodiment of the invention and its explanation for explaining only the invention, are not intended as to this
The restriction of invention.
Embodiment 1
Coating uses two-component system, with hundred parts of weight than weighing.
Component A resin is aliphatic epoxy resin.
Anti-corrosion pigments and fillers are several zinc powder mixtures of -1000 purpose of 300 mesh in component A.
Self-repair function additive is a kind of microballoon containing sustained release agent of homemade inorganic shell package in first component.Preparation
Method：In 200ml dehydrated alcohol, the hexadecyl trichlorosilane of 0.015g, ultrasound/stirring (stirring blade periphery linear speed are instilled
Spend 12 meter per seconds), it is slowly added to 5ml ethyl orthosilicate, after ultrasound/stirring (1 meter per second of stirring blade periphery linear velocity), successively
6ml ammonium hydroxide and water 50ml is added to filter after reaction 7 hours, washing, alcohol is washed, and 40 DEG C obtain a kind of Jie after vacuum drying 5 hours
Hole SiO 2 hollow microsphere, which, which is distributed to, (can be the complexing of this 179 organic zinc of SER-AD FA of hamming containing corrosion inhibiter
Object) 3% aqueous solution in, stirring (stirring blade periphery linear velocity 3-5 meter per second) disperse 2 hours after, stand 12 hours after, mistake
Filter obtains self-repair function additive after dry.
Mixed solvent refers to 10-30 parts of butyl acetate in component A, and 30-70 parts of dimethylbenzene mix.
Component B curing agent is one or more of 650 polyamide curing agents.
First and second components are with hundred parts of ratios of weight by epoxide equivalent: amine hydrogen equivalent=0.9: 1 is used in mixed way.
Embodiment 2
Design of Coatings Formulation uses two-component epoxy polyamide system.
It is 500 mesh/800 mesh=5/2 parts by weight mixing zinc powder that anti-corrosion pigments and fillers, which are partial size, in component A.
Self-repair function additive is a kind of microballoon containing sustained release agent of homemade Silica Shell package in first component.
Preparation method：In 200ml dehydrated alcohol, the hexadecyl trichlorosilane of 0.015g, ultrasound/stirring (stirring blade periphery are instilled
Linear velocity 1-2 meter per second), it is slowly added to 5ml ethyl orthosilicate, after ultrasound/stirring (1 meter per second of stirring blade periphery linear velocity),
It sequentially adds 6ml ammonium hydroxide and water 50ml, after reaction 7 hours, filters, washing, alcohol is washed, and 40 DEG C obtain one after vacuum drying 5 hours
Kind mesopore silica dioxide hollow sphere, which, which is distributed to, (can be this 179 organic zinc of SER-AD FA of hamming containing corrosion inhibiter
Complex compound) 3% aqueous solution in, stirring (stirring blade periphery linear velocity 3-5 meter per second) disperse 2 hours after, stand 12 hours
Afterwards, it filters, obtains self-repair function additive after dry.
Component B curing agent is 650 curing agent of one or more of epoxy resin.
First and second components are with hundred parts of ratios of weight by epoxide equivalent: amine hydrogen equivalent=0.9: 1 is used in mixed way.
Subsequent production technology is：
Component A technique is：Resin, self-repair function additive, solvent, auxiliary agent, pigment, filler are sequentially added into stirring
Pot, which is sanded after mixing evenly to fineness, reaches limit value, such as 40-60 microns, with corresponding solvent adjustment viscosity to restriction range
It is filtered and packaged after (2000-3000mpa.s).
Component B technique is：Range estimation curing agent state meets and can filter and package.
The first and second components are used in mixed way by corresponding proportion when coating decoration.
The present invention is only used as anti-corrosion primer to use, and also needs mating finishing coat in actual use, and recommending to select includes acrylic acid, fluorine
Various types of two-component coating systems such as carbon or polysiloxanes.Actual use coating typical case is mating to be：Priming paint 2, total dry film
120 microns of thickness.Finishing coat 2,100 microns of total thickness of dry film, per pass paint coating at least do solid work rear (25 DEG C, 24 hours) again
One of coating under coating.
The surface treatment of coated article must be up to standard, recommends to use airless spraying.
Comparative example 1
In the case where other preparation parameters remain unchanged, the composition of corrosion-inhibitive pigments is converted, is examined in neutral salt spray
It is tested respectively in (scratch), it is as a result as shown in table 1 with data analysis.
Corrosion resisting property compares under 1 coating damage state of table
The test result of comparative example 1 is it is known that the present invention was mixed using 500 mesh/800 mesh=5/2 parts by weight
Zinc powder, the time of resistance to neutral salt spray are considerably longer than the pigment of the zinc powder using same partial size, can be in the premise of control loading
Under, reach better conductive communication, with self-repair function additive obtain preferably match and synergistic action effect in, can
Improve the ply adhesion of coating and antirusting substrate paint.
Comparative example 2
In the case where other preparation parameters remain unchanged, the weight fraction of each component is converted, i.e. adjustment epoxide equivalent
It is as a result as shown in table 2 with data analysis respectively in neutral salt spray certification test with the ratio of amine hydrogen equivalent.
Corrosion resisting property compares under 2 coating serviceable condition of table
From the test result of comparative example 2 it is found that the first and second components that the present invention uses are worked as with hundred parts of ratios of weight by epoxy
Amount: amine hydrogen equivalent=0.9: 1 mixing match effect is substantially better than other several embodiments, in the time of neutral salt spray examination experience
Longest breaches 1200h, and the intact non-corroding of coating state, embodies the difference of effect.
Comparative example 3
Meanwhile the feelings that other preparation parameters remain unchanged are compared with embodiment 1 to above-mentioned two embodiment of the invention
Wetting dispersing agent is not only dosed under condition and compares what other preparation parameters remained unchanged with the embodiment 3 of levelling agent with embodiment 1
In the case of curing agent is only become into the embodiment 4 of T31 curing agent and embodiment 1 compares what other preparation parameters remained unchanged
In the case of only do not dose the embodiment 5 of auxiliary agent and embodiment 1 compare only will be molten in the case that other preparation parameters remain unchanged
Comprehensive parameter that agent becomes the embodiment 6 of butyl acetate is compared, and see Table 3 for details.
3 performance comparison tables of data of table
Meanwhile lots of comparing experiments is also shown that if wetting dispersing agent and levelling agent are not added in the process of production and processing, is applied
The appearance of layer will appear pin hole and dark bubble, and then intermiscibility, mobility and wetability is caused to be declined；Using polyamide 6 50
Or 650 epoxy curing agents, adhesive force, water resistance and flexible comprehensive performance are best, the solidification obtained after test
It is best with anticorrosion endurance；BYK auxiliary agent summarizes after all previous test and finds itself and self-repair function additive, corrosion-resistant face
The synergistic effect of material is best, and optimum results are best；Solvent is mixed using butyl acetate, dimethylbenzene, can sufficiently be adjusted pair
The volatile result of solubility and film of resin.
It is comprehensive well that performance test analysis through embodiment as above and comparative example shows that powder body material of the present invention has
Performance is closed, especially there is good salt spray resistance corrosion resistance.Anti-corrosion abrasion-resistant coating, is suitably applied provided by inventing
On metal material in harsh marine environment, pole can be brought to the service life of metal base or component in seawater is improved
Big improvement.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (4)
1. a kind of selfreparing anticorrosive paint, the anticorrosive paint uses the first and second bicomponent systems, and wherein first component includes asphalt mixtures modified by epoxy resin
Rouge, self-repair function additive, corrosion-inhibitive pigments, filler, auxiliary agent and solvent, second group are divided into curing agent,
It is characterized in that：Wherein, the self-repair function additive is micron order complex microsphere, and the shell of complex microsphere is two
Silica, shell is interior to load corrosion inhibiter, and corrosion inhibiter is benzo tetrazole or imidazoles beautiful jade or organozinc complex, and described is corrosion-resistant
Pigment be two or more partial sizes zinc powder, the filler be titanium dioxide, silica, the two or more mixing in mica powder and
At the auxiliary agent is BYK142 and/or BYK320, and the solvent is butyl acetate, dimethylbenzene mixes, and described consolidates
Agent is 650 curing agent of polyamide 6 50 or epoxy resin；
The parts by weight of said components are respectively：30-65 parts of epoxy resin, 5-30 parts of self-repair function additive, corrosion-inhibitive pigments
15-80 parts, 10-40 parts of filler, 0.1-3 parts of wetting dispersing agent, 0.1-3 parts of levelling agent, 10 30 parts of solvent, curing agent 70-80
Part, the first and second components are with hundred parts of ratios of weight by epoxide equivalent: amine hydrogen equivalent=0.9: 1 is used in mixed way；
Wherein, the method for preparing self-repair function additive is：In dehydrated alcohol, hexadecyl trichlorosilane, ultrasound are instilled
Stirring, stirring blade periphery linear velocity 1-2 meter per second are slowly added to ethyl orthosilicate, after ultrasonic agitation, stirring blade object-line
1 meter per second of speed, sequentially adds ammonium hydroxide and water, after reaction 7 hours, filters, and washing, alcohol is washed, and 40 DEG C after vacuum drying 5 hours
To mesopore silica dioxide hollow sphere, which is distributed in the aqueous solution containing corrosion inhibiter and is stirred, stirring blade periphery linear speed
3-5 meter per second is spent, after dispersion 2 hours, after standing 12 hours, filtering obtains self-repair function additive after dry.
2. selfreparing anticorrosive paint according to claim 1, it is characterised in that：The epoxy resin is aliphatic epoxy tree
Rouge.
3. selfreparing anticorrosive paint according to claim 1, it is characterised in that：The mixed solvent refers to 10 30 portions of vinegar
Acid butyl ester and 30-70 parts of dimethylbenzene mix.
4. selfreparing anticorrosive paint according to claim 4, it is characterised in that：Curing agent is one or more of polyamide
650 epoxy hardeners.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201810749642.XA CN108912960A (en) | 2018-07-10 | 2018-07-10 | A kind of selfreparing anticorrosive paint |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810749642.XA CN108912960A (en) | 2018-07-10 | 2018-07-10 | A kind of selfreparing anticorrosive paint |
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| CN108912960A true CN108912960A (en) | 2018-11-30 |
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| CN201810749642.XA Pending CN108912960A (en) | 2018-07-10 | 2018-07-10 | A kind of selfreparing anticorrosive paint |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110028824A (en) * | 2019-03-28 | 2019-07-19 | 华能国际电力股份有限公司海门电厂 | A kind of novel selfreparing Zinc-containing anticorrosion paint and preparation method thereof |
| CN111205745A (en) * | 2020-01-09 | 2020-05-29 | 厦门双瑞船舶涂料有限公司 | Self-repairing anticorrosive coating and preparation method thereof |
| CN115093774A (en) * | 2022-06-20 | 2022-09-23 | 广东智能涂料有限公司 | Automatic repair coating |
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| CN1766019A (en) * | 2005-09-22 | 2006-05-03 | 长江水利委员会长江科学院 | Nano composite aqueous epoxide resin coating material and preparation method |
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| CN106810993A (en) * | 2015-11-27 | 2017-06-09 | 中国科学院金属研究所 | Self-healing mould assembly epoxy coating and its preparation and application based on the mesoporous container of micron order |
| CN106905725A (en) * | 2017-04-13 | 2017-06-30 | 志合山海（北京）科技有限公司 | A kind of corrosion-inhibiting coating in application Yu Haiyang on metal-based layer and preparation method thereof |
| CN107201140A (en) * | 2017-06-17 | 2017-09-26 | 常州福隆工控设备有限公司 | A kind of self-healing coatings and preparation method thereof |
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| CN1766019A (en) * | 2005-09-22 | 2006-05-03 | 长江水利委员会长江科学院 | Nano composite aqueous epoxide resin coating material and preparation method |
| CN105017922A (en) * | 2014-04-16 | 2015-11-04 | 镇江德马化工有限公司 | Aqueous zinc-rich flake cathode protection prime coat, preparation method and uses thereof |
| CN106810993A (en) * | 2015-11-27 | 2017-06-09 | 中国科学院金属研究所 | Self-healing mould assembly epoxy coating and its preparation and application based on the mesoporous container of micron order |
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| CN110028824A (en) * | 2019-03-28 | 2019-07-19 | 华能国际电力股份有限公司海门电厂 | A kind of novel selfreparing Zinc-containing anticorrosion paint and preparation method thereof |
| CN111205745A (en) * | 2020-01-09 | 2020-05-29 | 厦门双瑞船舶涂料有限公司 | Self-repairing anticorrosive coating and preparation method thereof |
| CN115093774A (en) * | 2022-06-20 | 2022-09-23 | 广东智能涂料有限公司 | Automatic repair coating |
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Application publication date: 20181130 |