CN107619616A - A kind of graphene ultraviolet (UV) photocuring white coating and preparation method thereof - Google Patents
A kind of graphene ultraviolet (UV) photocuring white coating and preparation method thereof Download PDFInfo
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- CN107619616A CN107619616A CN201710880429.8A CN201710880429A CN107619616A CN 107619616 A CN107619616 A CN 107619616A CN 201710880429 A CN201710880429 A CN 201710880429A CN 107619616 A CN107619616 A CN 107619616A
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Abstract
The invention discloses a kind of graphene ultraviolet (UV) photocuring white coating, including following weight than raw material components：20~30 parts of UV cured silicones resin, 10~20 parts of bisphenol A epoxy acrylate resin of UV solidifications, 5~10 parts of ethylene glycol dimethacrylate, 5~10 parts of tripropylene glycol class diacrylate, 2; 4,6 5~10 parts of trimethyl benzoyl diphenyl base phosphine oxides, 3~5 parts of 1 hydroxycyclohexyl phenylketone, 5~10 parts of graphene oxide powder, 1~3 part of wetting dispersing agent, 1~3 part of UV absorbers, 10~20 parts of aluminium dioxide, 10~20 parts of titanium dioxide, 1~3 part of antimildew and antibacterial agent, 1~3 part of fluorine auxiliary agent.The white coating of the present invention can be weather-proof in instantaneous solidification film forming, resistant under action of ultraviolet radiation, green without organic volatile, non-environmental-pollution, can apply in tunnel and the engineering inner trim panels such as indoor/outdoor.
Description
Technical field
The present invention relates to a kind of composition and preparation method of graphene ultraviolet (UV) photocuring white coating, belongs to coating oil
Paint technical field.
Background technology
The long-term use of paint of the industries such as decorative board, calcium silicate board with microporous application, Tunnel Engineering is mainly traditional solvent-borne epoxy
Floor paint and solvent-borne type zinc rich primer antirust paint etc..This type paint passes through spraying application, and efficiency is low, time length to be done, cost
Height, environment is polluted, influence the health of workmen.And the hardness of traditional solvent-borne coating paint film is worn no resistance, ground in 2H or so
Consumption rate (g/100r) is higher than 0.15, and scratch resistance, paint film resistance to soiling are poor, and it is not easy to clean to speckle with oiliness color, and coating paint film product exists
Surface damage is easy in daily life.Secondly solvent based coating contains have an opportunity volatile matter and TDI toluene di-isocyanate(TDI)s, applies
Product can discharge harmful residual organic volatile after covering paint film film forming.
Graphene is a kind of individual layer chip architecture two-dimensional material being made up of carbon atom, be find so far it is most thin most hard
Material, there is maximum specific surface area, can infinitely be stretched, the link of the carbon atom of graphene is very flexible, it is former to apply external force carbon
Son can occur bending and deformation thus graphene has good stability, and oxidation-reduction method prepares that the graphene time is shorter, product
Purification step is simple, is current a kind of most commonly used method.Oxidation-reduction method is using graphite as raw material, first by graphite through oxygen
Change reaction into graphite oxide.By graphite dispersion in the acid of strong oxidizing property, add oxidant and obtain the graphite oxide hydrosol, by oxygen
Graphene oxide is obtained after the drying of the graphite hydrosol.
The most important advantage of UV photocureable coating technologies is higher production efficiency and lower energy consumption, quickly solidification
Speed, application is easy to operate, the operation under room temperature environment, alap VOC VOCs.China's coating industry
Propose that clear and definite environmental objective UV is coating material solidified, solvent-free in " 12 " development plan, what UV was coating material solidified in coating should
It is very wide with face, should be one of best coating variety of environmental protection and energy saving.
The content of the invention
It is an object of the invention to solve the above problems or defect, and provide the advantages of will be described later.
It is a still further object of the present invention to provide a kind of graphene ultraviolet (UV) photocuring resistant weatherability white coating, UV are solid
It is high to be melted into membrane substance solid content, is that one kind meets country's promotion environmental protection, energy-conservation, recycled without volatile organic compounds
Do not waste, efficient green coating.
It is a still further object of the present invention to provide a kind of preparation method of graphene ultraviolet (UV) photocuring white coating, its
Processing step is simple, and reaction condition is gentle, obtained white coating, and film-forming is quick, nonpollution environment, film is abundant meat
Feel, be as bright as a sixpence, there is excellent decorative effect, hence it is evident that improving coating efficiency.
In order to realize these purposes and further advantage of the invention, the invention provides a kind of graphene ultraviolet (UV) photocuring
White coating, it include following weight than raw material components：
20~30 parts of UV cured silicones resin, 10~20 parts of bisphenol A epoxy acrylate resin of UV solidifications, ethylene glycol two
5~10 parts of methacrylate, 5~10 parts of tripropylene glycol class diacrylate, 2,4,6- trimethyl benzoyl diphenyl base oxygen
Change 5~10 parts of phosphine, 1- hydroxyls -3~5 parts of cyclohexylbenzene ketone, 5~10 parts of graphene oxide powder, 1~3 part of wetting dispersing agent, purple
Outer 1~3 part of light absorber, 10~20 parts of aluminium dioxide, 10~20 parts of titanium dioxide, 1~3 part of antimildew and antibacterial agent, fluorine auxiliary agent 1~3
Part.
Preferably, the UV cured silicones resin contains 5 degrees of functionality, using Guangdong Boxing new material Co., Ltd
B-828 organic siliconresins, the resins synthesis, which introduces organosilicon, stronger resistance to yellow weather resistance, and reaction solidifies rapidly, without molten
Agent, high rigidity, wear-resisting scratch resistance, low surface tension, resistance to soiling are good.
Preferably, the graphene oxide powder is multi-layer graphene, and purity is more than 95%, 3.4~8nm of thickness, the number of plies
For 6~10 layers, oxygen content 0.5%, sulfur content 0.5%, metals content impurity 100ppm, specific surface area is less than 50m2/g.The oxygen
Graphite alkene powder uses the multi-layer graphene of Jiangsu Tan Feng graphenes Science and Technology Ltd..Graphene color powder is extensively and unique
Performance presents its great potential in metal material corrosion-resistant field.First, the stable sp of graphene2Hybrid structure can be
Physical barriers are formed between metal and active medium, prevent the progress of scattering and permeating；Secondly, graphene has good thermostabilization
Property and chemical stability, whether under the high temperature conditions (up to 1500 DEG C), or the gas with corrosion or oxidisability,
It can be kept in liquid environment stable.
Preferably, 5~7um of particle diameter of the aluminium dioxide.
Preferably, the antimildew and antibacterial agent is formed by nano anti-biotic material and organic safety efficient anti-fermenting agent compounding.Category
In the inorganic agent of non-release type, not permeable mistake, do not vacillate, will not also be consumed by Institute of Micro-biology, with special mechanical sterilization (surface
Processing), there is lasting fungus resistance, and there is unique safeguard function to microbial antibacterial, to prevent Institute of Micro-biology from drawing
The harm risen, extend leather, the service life of textile material, the novel mildew resistant processing as your antimildew and antibacterial scientific and technological developments of Ai Hao
Agent, it has extensive antibacterial activity.There is durability antibacterial effect to such as aspergillus, Chaetomium globosum and saccharomycete.
Preferably, the fluorine auxiliary agent is organic silicon-fluorine auxiliary agent, has stronger anti-soil hydrophobic performance.
Preferably, the raw material components of the graphene ultraviolet (UV) photocuring white coating also include 1~3 part of terminal hydroxy group
The mixture of polybutadiene or part polycarboxylic acids or both.
The UV absorbers are German BASF320, it is a kind of strong ultraviolet absorber, with a large amount of bases
Material has excellent compatibility.It can make polyester and organic pigment from the radiation of ultraviolet light, effectively keep injection-molded item, plastics thin
The outward appearance and physical property of film, plastic sheet.
A kind of method for preparing above-mentioned graphene ultraviolet (UV) photocuring white coating, comprises the following steps：
(1) successively by 1- hydroxyls alkane base Benzophenone, TMDPO, tripropylene glycol
Class diacrylate and ethylene glycol dimethacrylate are added in reaction vessel, 60 DEG C are warming up to, with rotating speed 1000rpm constant temperature
20min is stirred, obtains mixed liquor A；
(2) liquid A temperature to be mixed is down to normal temperature, sequentially add wetting dispersing agent, UV absorbers, antimildew and antibacterial agent,
Fluorine auxiliary agent, end hydroxy butadiene or polycarboxylic acids, after stirring 5min with rotating speed 1000rpm, add UV cured silicone resins
Solidify bisphenol-A epoxy acrylic resin with UV, control rotating speed 1200rpm is dispersed with stirring 10min, obtains mixed liquid B；
(3) powder graphene oxide powder, aluminium dioxide and titanium dioxide are slowly added to successively into mixed liquid B, powder adds
Control rotating speed 1500rpm is dispersed with stirring 30min after complete, then is ground to particle diameter fineness and is less than 15um, regulation viscosity to rotary viscosity
It is 1000 ± 100maps/25 DEG C to count 4# pins tested viscosity, that is, obtains graphene ultraviolet (UV) photocuring white coating.
Compared with prior art, the present invention is advantageous in that：
One, the present invention utilize high intensity, the graphene carbon material of high rigidity toughness, wear-resisting aluminium dioxide material, knot
Close UV photo-curable silicone resins and prepare graphene ultraviolet (UV) photocuring white coating, can be realized by ultraviolet photo-curing
Instantaneous solidification film forming, form hard, wear-resisting, anti-corrosion and extremely weather-proof paint film, it is possible to achieve mechanical intelligence application, efficiency improve,
UV film-forming material solid contents reach 99.5%, without volatile organic matter, be one kind meet country advocate environmental protection, energy-conservation,
Recycling does not waste, efficient green coating.The ultra-thin lamellar structure of graphene can form the physical isolation layer of densification, greatly
Amplitude improves the antiseptic effect of product, can apply the application of Tunnel Engineering decorative board and building decoration silico-calcium coated plate.
Secondly, added initiator TMDPO and 1- hydroxyls-ring in coating
Base Benzophenone, two kinds of initiator synergies are good and bad complementary, enough dissolvings with reactive diluent monomer energy so that coating exists
Under action of ultraviolet light can in 1 minute rapid curing film forming.
Thirdly, the end hydroxy butadiene of hydroxyl or carboxylic polycarboxylic acids are added in raw material components, this is in coating
Introduce polarity strong hydroxyl (- OH) or carboxyl (- COOH)；When the coating is coated in building surface, hydroxyl and carboxylic therein
Base and-Si-OH, the Ca contained in building surface cement mortar or concrete2+,-O-Si-O- produces bonding action and crosslinking is anti-
Should, make dope layer and building surface produce cohesion bonding action and it is embedding determine anchor conjunction, make coating and building surface formation skin
Formula seals, and strengthens the adhesive property of coating and ground, the problems such as avoiding coating cracking, peel, drop, and can also effectively prevent
Only channeling water phenomenon, durability and cold-resistant thermal impact are good, and antiseptic property is notable.
Further advantage, target and the feature of the present invention embodies part by following explanation, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Embodiment
The preferred embodiments of the present invention are illustrated below, it will be appreciated that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
Embodiment 1
The graphene ultraviolet (UV) photocuring white coating of the present invention is prepared, is concretely comprised the following steps：
(1) each raw material components are weighed：UV cured silicone resins 20kg, UV solidify bisphenol A epoxy acrylate resin
10kg, ethylene glycol dimethacrylate 5kg, tripropylene glycol class diacrylate 5kg, 2,4,6- trimethyl benzoyl diphenyls
Base phosphine oxide 5kg, 1- hydroxyl-cyclohexylbenzene ketone 3kg, graphene oxide powder 5kg, wetting dispersing agent 1kg, UV absorbers
1kg, aluminium dioxide 10kg, titanium dioxide 10kg, antimildew and antibacterial agent 1kg, fluorine auxiliary agent 1kg, end hydroxy butadiene 1kg；
(2) successively by 1- hydroxyls alkane base Benzophenone, TMDPO, tripropylene glycol
Class diacrylate and ethylene glycol dimethacrylate are added in reaction vessel, 60 DEG C are warming up to, with rotating speed 1000rpm constant temperature
20min is stirred, obtains mixed liquor A；
(3) liquid A temperature to be mixed is down to normal temperature, sequentially add wetting dispersing agent, UV absorbers, antimildew and antibacterial agent,
Fluorine auxiliary agent, end hydroxy butadiene, after stirring 5min with rotating speed 1000rpm, add UV cured silicones resin and UV solidifications
Bisphenol-A epoxy acrylic resin, control rotating speed 1200rpm are dispersed with stirring 10min, obtain mixed liquid B；
(4) powder graphene oxide powder, aluminium dioxide and titanium dioxide are slowly added to successively into mixed liquid B, powder adds
Control rotating speed 1500rpm is dispersed with stirring 30min after complete, then is ground to particle diameter fineness and is less than 15um, regulation viscosity to rotary viscosity
It is 1000 ± 100maps/25 DEG C to count 4# pins tested viscosity, that is, obtains graphene ultraviolet (UV) photocuring white coating.
Embodiment 2
The graphene ultraviolet (UV) photocuring white coating of the present invention is prepared, is concretely comprised the following steps：
(1) UV cured silicones resin 30kg, UV solidifies bisphenol A epoxy acrylate resin 20kg, ethylene glycol dimethyl
Acrylate 10kg, tripropylene glycol class diacrylate 10kg, TMDPO 10kg, 1-
Hydroxyl-cyclohexylbenzene ketone 5kg, graphene oxide powder 10kg, wetting dispersing agent 3kg, UV absorbers 3kg, aluminium dioxide
20kg, titanium dioxide 20kg, antimildew and antibacterial agent 3kg, fluorine auxiliary agent 3kg, polycarboxylic acids 3kg；
(2) successively by 1- hydroxyls alkane base Benzophenone, TMDPO, tripropylene glycol
Class diacrylate and ethylene glycol dimethacrylate are added in reaction vessel, 60 DEG C are warming up to, with rotating speed 1000rpm constant temperature
20min is stirred, obtains mixed liquor A；
(3) liquid A temperature to be mixed is down to normal temperature, sequentially add wetting dispersing agent, UV absorbers, antimildew and antibacterial agent,
Fluorine auxiliary agent, polycarboxylic acids, after stirring 5min with rotating speed 1000rpm, add UV cured silicones resin and UV solidification bisphenol-A epoxies
Acrylic resin, control rotating speed 1200rpm are dispersed with stirring 10min, obtain mixed liquid B；
(4) powder graphene oxide powder, aluminium dioxide and titanium dioxide are slowly added to successively into mixed liquid B, powder adds
Control rotating speed 1500rpm is dispersed with stirring 30min after complete, then is ground to particle diameter fineness and is less than 15um, regulation viscosity to rotary viscosity
It is 1000 ± 100maps/25 DEG C to count 4# pins tested viscosity, that is, obtains graphene ultraviolet (UV) photocuring white coating.
Embodiment 3
The graphene ultraviolet (UV) photocuring white coating of the present invention is prepared, is concretely comprised the following steps：
(1) UV cured silicones resin 25kg, UV solidifies bisphenol A epoxy acrylate resin 15kg, ethylene glycol dimethyl
Acrylate 8kg, tripropylene glycol class diacrylate 8kg, TMDPO 8kg, 1- hydroxyl
Base-cyclohexylbenzene ketone 4kg, graphene oxide powder 8kg, wetting dispersing agent 2kg, UV absorbers 2kg, aluminium dioxide
15kg, titanium dioxide 15kg, antimildew and antibacterial agent 2kg, fluorine auxiliary agent 2kg, end hydroxy butadiene and polycarboxylic acids are by weight 1:1 it is mixed
Compound 2kg；
(2) successively by 1- hydroxyls alkane base Benzophenone, TMDPO, tripropylene glycol
Class diacrylate and ethylene glycol dimethacrylate are added in reaction vessel, 60 DEG C are warming up to, with rotating speed 1000rpm constant temperature
20min is stirred, obtains mixed liquor A；
(3) liquid A temperature to be mixed is down to normal temperature, sequentially add wetting dispersing agent, UV absorbers, antimildew and antibacterial agent,
The mixture of fluorine auxiliary agent, end hydroxy butadiene and polycarboxylic acids, after stirring 5min with rotating speed 1000rpm, add UV and be solidified with
Machine silicones and UV solidification bisphenol-A epoxy acrylic resins, control rotating speed 1200rpm are dispersed with stirring 10min, obtain mixed liquid B；
(4) powder graphene oxide powder, aluminium dioxide and titanium dioxide are slowly added to successively into mixed liquid B, powder adds
Control rotating speed 1500rpm is dispersed with stirring 30min after complete, then is ground to particle diameter fineness and is less than 15um, regulation viscosity to rotary viscosity
It is 1000 ± 100maps/25 DEG C to count 4# pins tested viscosity, that is, obtains graphene ultraviolet (UV) photocuring white coating.
Graphene ultraviolet (UV) photocuring white coating prepared by above-mentioned 3 embodiments is provided into making sheet according to company standard
Examination criteria afterwards, as a result see the table below：
In summary, graphene ultraviolet (UV) photocuring white coating of the invention, can be realized by ultraviolet photo-curing
Instantaneous solidification film forming, form hard, wear-resisting, anti-corrosion and extremely weather-proof paint film, it is possible to achieve mechanical intelligence application, efficiency improve,
UV film-forming materials solid content is high, is that one kind meets country's promotion environmental protection, energy-conservation, recycled without volatile organic matter
Do not waste, efficient green coating.The ultra-thin lamellar structure of graphene can form the physical isolation layer of densification, increase substantially
The antiseptic effect of product, the application of Tunnel Engineering decorative board and building decoration silico-calcium coated plate can be applied.
The above described is only a preferred embodiment of the present invention, any formal limitation not is made to the present invention, though
So the present invention is disclosed above with preferred embodiment, but is not limited to the present invention, any to be familiar with this professional technology people
Member, without departing from the scope of the present invention, when the technology contents using the disclosure above make a little change or modification
For the equivalent embodiment of equivalent variations, as long as being the content without departing from technical solution of the present invention, the technical spirit according to the present invention
Any simple modification, equivalent change and modification made to above example, in the range of still falling within technical solution of the present invention.
Claims (8)
- A kind of 1. graphene ultraviolet (UV) photocuring white coating, it is characterised in that including following weight than raw material components：20~30 parts of UV cured silicones resin, 10~20 parts of bisphenol A epoxy acrylate resin of UV solidifications, ethylene glycol dimethyl 5~10 parts of acrylate, 5~10 parts of tripropylene glycol class diacrylate, TMDPO 5 ~10 parts, 1- hydroxyls -3~5 parts of cyclohexylbenzene ketone, 5~10 parts of graphene oxide powder, 1~3 part of wetting dispersing agent, ultraviolet light 1~3 part of absorbent, 10~20 parts of aluminium dioxide, 10~20 parts of titanium dioxide, 1~3 part of antimildew and antibacterial agent, 1~3 part of fluorine auxiliary agent.
- 2. graphene ultraviolet (UV) photocuring white coating as claimed in claim 1, it is characterised in that the UV solidifications are organic Silicones contains 5 degrees of functionality.
- 3. graphene ultraviolet (UV) photocuring white coating as claimed in claim 2, it is characterised in that the graphene oxide Powder is multi-layer graphene, and purity is more than 95%, and 3.4~8nm of thickness, the number of plies is 6~10 layers, oxygen content 0.5%, sulfur content 0.5%, metals content impurity 100ppm, specific surface area are less than 50m2/g。
- 4. graphene ultraviolet (UV) photocuring white coating as claimed in claim 3, it is characterised in that the aluminium dioxide 5~7um of particle diameter.
- 5. graphene ultraviolet (UV) photocuring white coating as claimed in claim 4, it is characterised in that the antimildew and antibacterial agent Formed by nano anti-biotic material and organic safety efficient anti-fermenting agent compounding.
- 6. graphene ultraviolet (UV) photocuring white coating as claimed in claim 5, it is characterised in that the fluorine auxiliary agent is to have Machine fluosilicic auxiliary agent.
- 7. graphene ultraviolet (UV) photocuring white coating as claimed in claim 1, it is characterised in that the raw material components are also Include the mixture of 1~3 part of end hydroxy butadiene or polycarboxylic acids or both.
- 8. a kind of preparation method of graphene ultraviolet (UV) photocuring white coating as described in claim 1~7 any one, It is characterised in that it includes following steps：(1) successively by 1- hydroxyls alkane base Benzophenone, TMDPO, tripropylene glycol class two Acrylate and ethylene glycol dimethacrylate are added in reaction vessel, are warming up to 60 DEG C, constant temperature stirring 20min, are mixed Close liquid A；(2) liquid A temperature to be mixed is down to normal temperature, sequentially adds wetting dispersing agent, UV absorbers, antimildew and antibacterial agent, fluorine and helps Agent, end hydroxy butadiene or polycarboxylic acids, after being dispersed with stirring uniformly, add UV cured silicones resin and UV solidification bisphenol-As Epoxy acrylic resin, control rotating speed 1200rpm are dispersed with stirring 10min, obtain mixed liquid B；(3) powder graphene oxide powder, aluminium dioxide and titanium dioxide are slowly added to successively into mixed liquid B, after powder has added Control rotating speed 1500rpm is dispersed with stirring 30min, then is ground to particle diameter fineness and is less than 15um, regulation viscosity to rotation viscometer 4# Pin tested viscosity is 1000 ± 100maps/25 DEG C, that is, obtains graphene ultraviolet (UV) photocuring white coating.
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| CN110863343A (en) * | 2019-11-27 | 2020-03-06 | 浙江圣山科纺有限公司 | Environment-friendly ultraviolet-resistant finishing agent and outdoor cloth using same |
| CN116855155A (en) * | 2023-07-06 | 2023-10-10 | 华南理工大学 | Electrostatic spinning film-epoxy resin coating and preparation method and application thereof |
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| CN109401599A (en) * | 2018-09-12 | 2019-03-01 | 安徽康瑞高科新材料技术工程有限公司 | A kind of UV coating and preparation method thereof suitable for BMC |
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| CN116855155A (en) * | 2023-07-06 | 2023-10-10 | 华南理工大学 | Electrostatic spinning film-epoxy resin coating and preparation method and application thereof |
| CN116855155B (en) * | 2023-07-06 | 2023-12-12 | 华南理工大学 | Electrostatic spinning film-epoxy resin coating and preparation method and application thereof |
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