CN104327721B - Nano-antibacterial low surface energy organic silicon luminescence antifouling paint and preparation method thereof - Google Patents
Nano-antibacterial low surface energy organic silicon luminescence antifouling paint and preparation method thereof Download PDFInfo
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- CN104327721B CN104327721B CN201410545977.1A CN201410545977A CN104327721B CN 104327721 B CN104327721 B CN 104327721B CN 201410545977 A CN201410545977 A CN 201410545977A CN 104327721 B CN104327721 B CN 104327721B
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Abstract
The invention discloses nano-antibacterial low surface energy organic silicon luminescence antifouling paint, described coating includes the third component of the first component of 25～35 parts, the component B of 2～5 parts and 1 part by weight；First component includes by weight: nano fluorescent predispersion 25.0～50.0 parts；Organosilicon quaternary ammonium salt 5～25.0 parts；Silicone oil 0.5～5.0 parts；Component B includes by weight: crosslinking and curing agent 3.0～50.0 parts；Silane coupler 1.0～10.0 parts；Third component includes by weight: catalyst 0.1～3.0 parts；Described catalyst is at least one in stannous octoate, dibutyltin diacetate, dibutyl tin dilaurate.This coating has a long-persistence luminous performance, relies on that fluorescence is antifouling, contact sterilization, has that antifouling property is excellent, intensity is high, adhesive force advantages of higher, can apply to various boats and ships, offshore platform, marine structure and facility, mariculture netting gear etc..
Description
Technical field
The invention belongs to luminous paint, staining-proof coating, antifouling paint, underwater coating compound technical field, be specifically related to receive
Nano antibacterial low surface energy organic silicon luminescence antifouling paint and preparation method thereof.
Background technology
The halobiontic problem that is stained limits people to the development and utilization of marine resources, the attachment of various marine growths always
Ship resistance can be caused to increase, and Fuel Consumption increases, and ship is caused corrosion, meeting by the metabolite of marine growth
Increase boats and ships maintenance cost, reduce ship in boat rate, marine growth also can block the various pipeline in seabed, valve and support
Growing the mesh of net cage, the economic loss caused is difficult to estimate.In order to realize preventing and kill off halobiontic, the antifouling painting of application
Material is to solve the not only economy but also efficient important channel that the problem that is stained uniquely is used widely.But, currently used
Many antifouling paints, releasable antifouling toxic agent (such as organotin, Red copper oxide) contained by it can cause Marine water dirty
Dye, causes biomutation, jeopardizes marine food chain, and marine ecology balance and human health are had potential hazard.
Therefore, International Maritime Organization (IMO) the 21st session determines, will thoroughly prohibit the use of after on January 1st, 2008
Antifouling paint containing organotin.For this situation, exploitation Wuxi, nontoxic environmental protection antifouling paint become antifouling paint
Developing direction.
Low surface energy anti-fouling paint comes off type antifouling paint also known as waste, rely on coating have low surface can, not only
Can reduce and stop the attachment of various marine growth, and environmentally friendly, nonhazardous, the viscosity of water can be significantly reduced again
Frictional resistance, is the most promising a kind of boats and ships nontoxic anti-fouling anti-drag coating materials, receive both domestic and external extensively
Pay close attention to.Calculate according to international paint companies[27], use low surface energy anti-fouling paint and use the tradition poison material antifouling painting of release type
Material is compared, and boats and ships need the antifouling paint volume of application can reduce 80%, and VOC noxious volatile gas discharges minimizing 90%,
Poison material minimizing 100%, marine fuel oil consumption and the greenhouse gases (CO of equivalence2) discharge minimizing 4-9%.Low-surface-energy is antifouling
The research and development of coating relate generally to organosilicon and fluoropolymer two class.Organic silicon antifouling paint experienced by from organic silicon rubber
To the R&D process of modified linear polysiloxanes, substantial amounts of research shows, although anti-fouling effect is the best, but organosilicon
Antifouling paint demonstrates fouling organism removal effect more more preferable than fluorine carbon antifouling paint.Study accordingly, as product development,
The attention of the international well-known paint company of organic silicon antifouling paint Geng Shou, puts into huge sum of money exploitation in succession with polydimethylsiloxane
Product is had to push city to for only a few manufacturers such as the low surface energy anti-fouling paints of base material, the most only Britain international standard paint company
?.Although low surface energy anti-fouling paint is still within the research and development stage, but the application of low surface energy anti-fouling paint is just
Constantly expanding, presenting the trend progressively substituting self polishing copolymer antifouling paint, represented the developing direction of antifouling paint.
In a word, owing to organic silicon antifouling paint has huge application prospect, all the time by Chinese scholars, each big coating public affairs
The concern of department.
Although there being some low surface energy anti-fouling paints to come into the market, antifouling for high-speed ship.But a large amount of real ships should
With showing, owing to boats and ships suspending time is longer, marine growth is still able to be attached in a large number hull bottom, needs periodic cleaning, attached
Thing once to grow up and would become hard to remove, thus make its range of application be subject to certain restrictions.
Summary of the invention
Urgent needs, low surface energy anti-fouling paint for domestic and international environmentally friendly marine antifouling anti-drag paint exist
The problem that antifouling property is not enough, the present invention provides a kind of nano-antibacterial low surface energy organic silicon luminescence antifouling paint, this painting
Material has a long-persistence luminous performance, relies on that fluorescence is antifouling, contact sterilization, has that antifouling property is excellent, intensity is high, attached
Put forth effort advantages of higher, can apply to various boats and ships, offshore platform, marine structure and facility, mariculture
Netting gear etc..
The technical solution of the present invention is: nano-antibacterial low surface energy organic silicon luminescence antifouling paint, wraps by weight
Include the third component of the first component of 25～35 parts, the component B of 2～5 parts and 1 part；
First component includes by weight:
Nano fluorescent predispersion 25.0～50.0 parts；
Organosilicon quaternary ammonium salt 5～25.0 parts；
Silicone oil 0.5～5.0 parts；
Component B includes by weight:
Crosslinking and curing agent 3.0～50.0 parts；
Silane coupler 1.0～10.0 parts；
Third component includes by weight:
Catalyst 0.1～3.0 parts；
Described catalyst is at least one in stannous octoate, dibutyltin diacetate, dibutyl tin dilaurate.
Described nano fluorescent predispersion is nano titanium oxide and fluorescent powder is dispersed in polysiloxanes by following weight portion
In resin；
Nano titanium oxide 2～5 parts；
Fluorescent powder 5～30 parts；
Polyorganosiloxane resin 50～70 parts.
The particle size range of nano titanium oxide is chosen as 10-100nm, preferably 10-50nm.
The particle diameter of fluorescent powder is preferably 5～65 microns, more preferably 25～40 microns.
Preferably, described nano fluorescent predispersion also includes:
Solvent 5～15 parts；
Dispersant 0.5～1 part；
Described solvent be described solvent be at least one in ketone, alcohols, aromatic hydrocarbon, esters.
Preferably, described polyorganosiloxane resin is α, alpha, omega-dihydroxy polysiloxanes, α, alpha, omega-dihydroxy polydimethyl
Siloxanes, α, at least one in alpha, omega-dihydroxy methyl silicone resins；
Described crosslinking and curing agent be tetraethyl orthosilicate, methyl triacetoxysilane, containing alkoxyl, amino, amide groups,
At least one in the silane of oximido or ketone group；
Described silane coupler is gamma-aminopropyl-triethoxy-silane (KH550), γ-(2,3-glycidyl) propyl group
Trimethoxy silane (KH560), N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (KH792), γ-(first
Base acryloyl-oxy) at least one in propyl trimethoxy silicane (KH570).
Preferably, described silicone oil be described silicone oil be nonactive silicone oil.Be preferably methyl-silicone oil, methyl phenyl silicone oil or
Methyl Hydrogen Polysiloxane Fluid.
Preferably, described organosilicon quaternary ammonium salt is quaternary ammonium salt cationic surfactant.
Preferably, organosilicon quaternary ammonium salt is the polysiloxane compound of band positive charge, is a class quaternary ammonium salt cationic surface
Activating agent, its general structure is:
In formula, R is the group that can hydrolyze, such as-OC2H5With-OCOOCl etc.；R1For alkyl, oxygen-containing or nitrogen-containing group, such as-CH2-、
-CH2COCH2CH2-、-(CH2)3NCH2CH2-etc.；R2For the alkyl containing 1～20 carbon atom；X is acid radical anion.
As preferred technical scheme, described first component the most also includes:
White filler 1.0～25.0 parts
Auxiliary agent 0.5～5.0 parts
Described auxiliary agent is at least one in dispersant, defoamer, levelling agent, surfactant；
Described white filler be in dicalcium powder, Pulvis Talci, barium sulfate, aluminium oxide, Kaolin, titanium white, zinc white at least
A kind of.Described white filler is preferably the titanium dioxide of high covering power.
Wherein the available kind of auxiliary agent is respectively as follows:
Dispersant: at least one in BYK161, BYK163, De Qian company of Bi Ke company 903,9250,931；
Defoamer: at least one in Bi Ke company BYK066N, moral modest 5600,5800,6600；
Levelling agent: Bi Ke company BYK358, enlightening are high by 435, moral modest 435,433,837 at least one.
As preferred technical scheme,
Described first component the most also includes:
Solvent 0.0～30.0 parts；
Described component B the most also includes:
Solvent 0.0～20.0 parts；
Described third component the most also includes:
Solvent 0.4～10.0 parts；
Described solvent is at least one in ketone, alcohols, aromatic hydrocarbon, esters.
Solvent of the present invention be preferably pentanedione, acetone, butanone, hexone, dehydrated alcohol, toluene,
In dimethylbenzene at least one.
The present invention also provides for the preparation method of above-mentioned nano-antibacterial low surface energy organic silicon luminescence antifouling paint, by described first,
Second, the third three components, by described weight portion mix homogeneously, obtain after crosslinked solidification.
Preferably, the mixed method of described first component is: join in dispersion machine by each constituent of first component, with
Speed dispersed with stirring 30min of 1000～2000 revs/min, then treats after sand mill sand milling to fineness is less than 40 μm
With.
Preferably, described nano fluorescent predispersion prepares by the following method: first by polyorganosiloxane resin, solvent
Add in dispersion machine with dispersant and be uniformly mixed, add nano titanium oxide and divide at a high speed under 4000～5000rpm
Dissipate 30min, be subsequently adding fluorescent powder and continue high speed dispersion 15min.
The marine antifouling coating using technique scheme to make, can use the method constructions such as brushing, spraying or roller coating,
Stir evenly before using, can be according to purposes and environment solvent adjustment viscosity.
The method of the present invention be a kind of synthesize conveniently, practical method, involved basic raw material can be very convenient
Commercially buy.
The marine antifouling coating of the present invention is applied to the soiling protective of boats and ships, marine structure, and having coating surface can be low,
Marine growth is not easy to attachment, though attachment also easily self falling or the feature that is easily eliminated.And can be to set under water
Execute, pipeline etc. provides the effects such as mark, sign.
The present invention by scientifically designing the formula of organic silicon low-surface-energy antifouling paint, priority control organosilicon quaternary ammonium salt,
The content of the fillers such as the content of nano titanium oxide, fluorescent powder, silicone oil etc. and titanium dioxide, triple superphosphate, barium sulfate,
Realize that quaternary ammonium salt contact sterilization is antifouling, photochemical catalytic oxidation sterilization is antifouling, long-afterglow fluorescent is antifouling, the antifouling decontamination of silicone oil,
The multiple collaborative antifouling purposes such as low-surface-energy is antifouling；Nano titanium oxide is improving the same of the long-persistence luminous performance of coating
Time, improving its intensity and antifraying property, the surface topography of structure micro nano structure improves the antifouling of coating further and subtracts
Resistive energy.Thus novel nano antimicrobial organosilane low-surface-energy marine antifouling anti-drag paint is prepared in exploitation, green for sea
Color traffic provides technical support.
Beneficial effects of the present invention shows:
1. the present invention first passes through high speed shear dispersion and prepares nano fluorescent predispersion, and its favorable attributes outstanding behaviours is can
Nano titanium oxide and fluorescent powder with thorough depolymerization secondary agglomeration, it is thus achieved that nano titanium oxide and fluorescent powder are abundant
The nano fluorescent predispersion being dispersed in polyorganosiloxane resin.Nano titanium oxide and fluorescent powder homogeneous blend,
There is the potentiation improving the long-persistence luminous performance of fluorescent powder, strengthen the fluorescence antifouling property of coating, to detesting light
Marine animal (particularly barnacle) larva has significant anti-fouling effect.
2. the silane coupler contained in the antifouling paint of the present invention, provides the knot excellent with ground for coating of the present invention
Make a concerted effort so that coating of the present invention can directly be painted on the conventional epoxy primer of shipping industry coating, epoxy intermediate coat,
Reduce application passage, reduce the difficulty of construction of supporting application；The duration is repaiied in the depressed place saving boats and ships.
3. the antifouling paint of the present invention contains the little molecule silicone oil of a certain amount of reactionless activity, the clothes after paint solidification
During labour, due to the effect of interfacial tension, it can gradually migrate the activated interface being discharged into coating with sea water, is formed
The silicon oil membrane that one layer of soft stick-slip is unstable, on the one hand reduces the marine growth attachment at hull surface, the most permissible
Significantly weaken the adhesion of attachment marine growth and hull coatings so that attachment marine growth is prone under the souring of sea water
Self falling, has excellent anti-fouling anti-drag performance.
4. the antifouling paint smooth surface of the present invention, has minimizing ship resistance, reduces marine fuel oil consumption and temperature
The effect of room gas discharge.
5. the antifouling paint of the present invention contains a certain amount of nano titanium oxide so that coating not only has excellent light and urges
Change sterilization antifouling property, and there is excellent mechanical property and higher hardness, it is ensured that coating has higher wear-resistant
And anti-scuffing function.
6. the antifouling paint of the present invention contains a certain amount of organosilyl quaternary ammonium salt sterilizing agent, and it is solid with organic siliconresin crosslinking
After change, be uniformly distributed in the coating with the form of segment, when with the marine organisms larva of anion or spore near being coated with
During layer surface, the anion binding that the quaternary ammonium salt cationic of coating surface and marine organisms cell are carried, cause cell quilt
Destroy, play the purpose that contact sterilization is antifouling, and harmful substance will not be discharged in marine environment.
Detailed description of the invention
Embodiment is set forth below, and the present invention will be described, but the present invention is not limited by following embodiment, is meeting this
Can make various changes in the range of objective before and after invention, these are included in the technical scope of the present invention.
The α that the present invention selects, alpha, omega-dihydroxy polydimethyl siloxane is purchased from Shandong Dayi Chemical Industry Co., Ltd, DY-107
Silicone rubber, viscosity (25 DEG C): 2500～1000000mPa s, the α of different viscosities, ω-dihydroxy can be selected as required
Base polydimethylsiloxane, the mainly viscosity used in the embodiment of the present invention be respectively 2800mPa s and
The α of 10000mPa s, alpha, omega-dihydroxy polydimethyl siloxane, but implement the present invention selected polyorganosiloxane resin,
It is not limited to producer and specific performance parameter thereof.
The silicate luminescent that the fluorescent powder that described invention is selected produces purchased from MingFa optical Science Co., Ltd., DaLian Road
Material (blue colour fluorescent powder SB-8C), alkaline earth aluminates phosphors (yellowish green fluorescent powder PLO-7C), alkaline earth aluminosilicate
Salt luminescent material (yellowish green fluorescent powder SP-4).But implement the present invention selected fluorescent powder, be not limited to producer and
Its specific performance parameter.
The organosilicone quaternary ammonium that the organosilicon quaternary ammonium salt that described invention is selected produces purchased from Guangzhou Nuokang Chemical Co., Ltd.
Salt, particular chemical [(CH3CH2O)3Si(CH2)3N+(CH3)2C18H37]Cl-.But implement the present invention selected organic
Silicon quaternary ammonium salt, is not limited to producer and specific performance parameter thereof.
The nano titanium oxide that described invention is selected is the P25 mixed crystal type nanometer titanium dioxide purchased from Beyer Co., Ltd's sale, Ji
The nanometer anatase titania of south abundant Xinghua work production and sales.The present invention select titanium dioxide be not limited to producer and
Specific performance parameter, can be selected for having the anatase titanium dioxide of photocatalytic effect, rutile-type or mixed crystal type nanometer titanium dioxide.
Embodiment 1
The most first by the α of 70 parts of viscosity 10000mPa s, alpha, omega-dihydroxy polydimethyl siloxane, 1 part of dispersant
In the dispersion tank of BYK161,10 parts of dimethylbenzene and 3 parts of domestic nanometer anatase titania addition dispersion machines,
High speed dispersion 30min under 4000rpm, is subsequently adding 16 parts of blue colour fluorescent powder SB-8C and continues high speed dispersion 15min,
Prepare nano fluorescent predispersion.
Each constituent is joined in the dispersion tank of dispersion machine by first component the most successively, with the speed of 2000 revs/min
High-speed stirred dispersion 30min, then canned stand-by after sand mill sand milling to fineness is less than 40 μm.
Component B and the third component are respectively according to canned stand-by after proportioning mix homogeneously.
According to first before using: the ratio mixing and stirring of second: third=30:4:1, after application, solidification, obtain organosilicon
Low-surface-energy nonpolluting coating.
First component forms:
Component B forms:
Tetraethyl orthosilicate 5.0 parts
Silane coupling agent KH550 3.0 parts
Dimethylbenzene 11.0 parts
Third component composition:
February acetic acid dibutyl tin 1.0 parts
Pentanedione 9.0 parts
Embodiment 2
The most first by the α of 60 parts of viscosity 10000mPa s, alpha, omega-dihydroxy polydimethyl siloxane, 1 part of dispersant
In the dispersion tank of BYK161,8 parts of dimethylbenzene and 2 parts of domestic nanometer anatase titania addition dispersion machines, at 4000rpm
Lower high speed dispersion 30min, is subsequently adding 10 parts of yellowish green fluorescent powder SP-4 and continues high speed dispersion 15min, prepare nanometer
Fluorescence predispersion.
Each constituent is joined in the dispersion tank of dispersion machine by first component the most successively, with the speed of 1500 revs/min
High-speed stirred dispersion 30min, then canned stand-by after sand mill sand milling to fineness is less than 40 μm.
Component B and the third component are respectively according to canned stand-by after proportioning mix homogeneously.
According to first before using: the ratio mixing and stirring of second: third=25:4:1, obtain organic after application, solidification
Silicon low-surface-energy nonpolluting coating.
First component forms:
Component B forms:
Tetraethyl orthosilicate 5.0 parts
Silane coupler KH560 3.0 parts
Dehydrated alcohol 11.0 parts
Third component composition:
Dibutyl tin laurate 3.0 parts
7.0 parts of acetone
Embodiment 3
The most first by the α of 50 parts of viscosity 10000mPa s, alpha, omega-dihydroxy polydimethyl siloxane, 20 parts of viscosity
The α of 2800mPa s, alpha, omega-dihydroxy polydimethyl siloxane, 1 part of dispersant B YK161,10 parts of dimethylbenzene and 3
The domestic nanometer anatase titania of part adds in the dispersion tank of dispersion machine, high speed dispersion 30min under 4500rpm,
It is subsequently adding 16 parts of yellowish green fluorescent powder SP-4 and continues high speed dispersion 15min, prepare nano fluorescent predispersion.
Each constituent is joined in the dispersion tank of dispersion machine by first component the most successively, with the speed of 1800 revs/min
High-speed stirred dispersion 30min, then canned stand-by after sand mill sand milling to fineness is less than 40 μm.
Component B and the third component are respectively according to canned stand-by after proportioning mix homogeneously.
According to first before using: the ratio mixing and stirring of second: third=35:5:1, obtain organic after application, solidification
Silicon low-surface-energy nonpolluting coating.
First component forms:
Component B forms:
Tetraethyl orthosilicate 5.0 parts
Silane coupler KH560 3.0 parts
Dehydrated alcohol 11.0 parts
Third component composition:
Dibutyl tin laurate 3.0 parts
Pentanedione 7.0 parts
Embodiment 4
The most first by the α of 55 parts of viscosity 10000mPa s, alpha, omega-dihydroxy polydimethyl siloxane, 0.5 part of dispersion
In the dispersion tank of agent BYK163,5 parts of dimethylbenzene and 4 parts of import P25 nano titanium oxide addition dispersion machines, at 4000rpm
Lower high speed dispersion 30min, is subsequently adding 18 parts of yellowish green fluorescent powder SP-4 and continues high speed dispersion 15min, prepare nanometer
Fluorescence predispersion；
Each constituent is joined in the dispersion tank of dispersion machine by first component the most successively, with the speed of 1200 revs/min
High-speed stirred dispersion 30min, then canned stand-by after sand mill sand milling to fineness is less than 40 μm.
Component B and the third component are respectively according to canned stand-by after proportioning mix homogeneously.
According to first before using: the ratio mixing and stirring of second: third=25:2:1, obtain organic after application, solidification
Silicon low-surface-energy nonpolluting coating.
First component forms:
Component B forms:
Tetraethyl orthosilicate 5.0 parts
Silane coupler KH570 3.0 parts
11.0 parts of acetone
Third component composition:
Dibutyl tin laurate 3.0 parts
Dimethylbenzene 7.0 parts
Embodiment 5
The most first by the α of 65 parts of viscosity 10000mPa s, alpha, omega-dihydroxy polydimethyl siloxane, 0.8 part of dispersion
In the dispersion tank of agent BYK161,10 parts of dimethylbenzene and 3 parts of import P25 nano titanium oxide addition dispersion machines,
High speed dispersion 30min under 4000rpm, is subsequently adding 30 parts of yellowish green fluorescent powder PLO-7C and continues high speed dispersion 15min,
Prepare nano fluorescent predispersion.
Each constituent is joined in the dispersion tank of dispersion machine by first component the most successively, with the speed of 1500 revs/min
High-speed stirred dispersion 30min, then canned stand-by after sand mill sand milling to fineness is less than 40 μm.
Component B and the third component are respectively according to canned stand-by after proportioning mix homogeneously.
According to first before using: the ratio mixing and stirring of second: third=30:4:1, obtain organic after application, solidification
Silicon low-surface-energy nonpolluting coating.
First component forms:
Component B forms:
Tetraethyl orthosilicate 5.0 parts
Silane coupler KH792 3.0 parts
Dimethylbenzene 11.0 parts
Third component composition:
Dibutyl tin laurate 3.0 parts
Pentanedione 7.0 parts
Embodiment 6
The most first by the α of 50 parts of viscosity 10000mPa s, alpha, omega-dihydroxy polydimethyl siloxane, 30 parts of viscosity
The α of 2800mPa s, alpha, omega-dihydroxy polydimethyl siloxane, 1 part of dispersant B YK161,5 parts of dimethylbenzene and 4 parts
Import P25 nano titanium oxide adds in the dispersion tank of dispersion machine, high speed dispersion 30min under 5000rpm, then
Add 20 parts of yellowish green fluorescent powder PLO-7C and continue high speed dispersion 15min, prepare nano fluorescent predispersion.
Each constituent is joined in the dispersion tank of dispersion machine by first component the most successively, with the speed of 3500 revs/min
High-speed stirred dispersion 30min, then canned stand-by after sand mill sand milling to fineness is less than 40 μm.
Component B and the third component are respectively according to canned stand-by after proportioning mix homogeneously.
According to first before using: the ratio mixing and stirring of second: third=28:3:1, obtain organic after application, solidification
Silicon low-surface-energy nonpolluting coating.
First component forms:
Component B forms:
Tetraethyl orthosilicate 5.0 parts
Silane coupler KH792 3.0 parts
Dehydrated alcohol 11.0 parts
Third component composition:
Dibutyl tin laurate 2.0 parts
Pentanedione 8.0 parts
Embodiment 7
The most first by the α of 20 parts of viscosity 10000mPa s, alpha, omega-dihydroxy polydimethyl siloxane, 30 parts of viscosity
The α of 2800mPa s, alpha, omega-dihydroxy polydimethyl siloxane, 1 part of dispersant B YK161,5 parts of dimethylbenzene and 5 parts
Import P25 nano titanium oxide adds in the dispersion tank of dispersion machine, high speed dispersion 30min under 4500rpm, then
Add 25 parts of yellowish green fluorescent powder PLO-7C and continue high speed dispersion 15min, prepare nano fluorescent predispersion.
Each constituent is joined in the dispersion tank of dispersion machine by first component the most successively, with the speed of 5000 revs/min
High-speed stirred dispersion 30min, then canned stand-by after sand mill sand milling to fineness is less than 40 μm.
Component B and the third component are respectively according to canned stand-by after proportioning mix homogeneously.
According to first before using: the ratio mixing and stirring of second: third=28:4:1, obtain organic after application, solidification
Silicon low-surface-energy nonpolluting coating.
First component forms:
Defoamer (moral modest 6800) 0.5 part
Dimethylbenzene 10.0 parts
Component B forms:
Tetraethyl orthosilicate 5.0 parts
Silane coupler KH792 3.0 parts
Dimethylbenzene 11.0 parts
Third component composition:
Dibutyl tin laurate 3.0 parts
Pentanedione 7.0 parts
Coating property assay method and result
Hard to the surface water contact angle of coating model, diiodomethane contact angle, surface free energy, elastic modelling quantity, shore
Degree and antifouling property are measured, and assay method is as follows, and measurement result is as shown in table 1.
1. contact angle
Use the JC2000 type contact angle instrument testing coating table that Shanghai Zhongchen digital technology equipment Co., Ltd produces
The contact angle in face.Connect 2 μ l deionized waters or diiodomethane to drip and test after 10 seconds in coating surface, each painting
Layer model takes 3 points of distance 5mm mutually and takes pictures, and then uses goniometry to measure left and right contact angle respectively, altogether
6 readings, average as measured value.
2. surface can be estimated
Measure water contact angle and the diiodomethane contact angle of film respectively, after obtaining meansigma methods, substitute into following formula gauging surface
Can:
Wherein,It is respectively water contact angle and the diiodomethane contact angle of this coating.
3. elastic modelling quantity
In order to measure the elastic modelling quantity of coating, Teflon mould injection molding is utilized to prepare long 120mm, wide 60mm, thickness
2mm sample, cuts into tensile sample (long 50mm, wide 15mm, thick 2mm), uses Jinan blue streak electromechanics factory to produce
XLW type electronics tension tester measures the stress strain curve of coating, calculates elastic modelling quantity, and rate of extension is 25mm/min.
The thickness of the front typing sample of stretching and width, thickness uses vernier caliper measurement testing bar two ends and centre position thickness
Average, calculates its cross-sectional area, records tensile sample data, can obtain the springform of sample by analyzing this curve
Amount.Each coating is tested 3 times, averages.
Elastic modelling quantity is stress-strain diagram slope, its computational methods such as following formula, and unit is MPa.
Wherein, b, d are the initial width of sample and thickness, L0For the initial length of sample stretch zones, L is for being subject to
The length of stretch zones during power F.
4. shore hardness
The shore hardness of coating is measured with HT220 Shore A durometer.Method particularly includes: fold to protect by injection molded specimens
Card durometer probe is not affected by other body surface hardness in addition to injection molded specimens as far as possible, takes three diverse locations to measure
And take its meansigma methods.
5. antifouling property test
Link plate preparation and Dalian Sea Area is carried out according to standard GB/T 5370-85 anti-fouling paint model shallow sea soak test method
Shallow sea board experiment, evaluates the antifouling property of coating.Test carry out in Port Arthur landing stage, on model framework edge and
Lower edge is dipped in the sea water away from sea level 0.5m to 2m respectively.Carrying out link plate every month and observe inspection, test and appraisal are biological attached
Degree.Link plate utilizes CB-8L-C hand-driven pressure to exempt from cut Multifunctional car washer after 3 months, under 2Bar pressure,
Nozzle distance specimen surface about 10cm, after the aufwuch of water jet douche specimen surface, evaluates fouling release difficulty or ease
The apparent condition of coating after degree and removing.
6. coating color
The color of coating and fluorescence color visual evaluation.
The most long-persistence luminous illumination
The tinplate of about 50 micron thickness coatings will be scribbled in fixed light source (daylight lamp intensity of illumination 133.5 during experiment
Lux, plate identity distance fluorescent tube height is 55.5cm) under illumination 5min, be then shut off daylight lamp, the most in dark conditions
The ST-900 type faint light photometer/radiometer measurement illumination using Aobodi Photoelectric Technology Co., Ltd., Beijing to produce is strong
Degree, is shown in Table 1 instrument readings as measurement result.
Table 1. embodiment 1-7 coating performance and state
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| Water contact angle (°) | 114.25 | 112 | 111.08 | 110.83 | 115.83 | 113.67 | 111.08 |
| Diiodomethane contact angle (°) | 72.92 | 79 | 75.08 | 72.75 | 75.42 | 72.08 | 79.08 |
| Surface can (mJ/m2) | 21.91 | 18.08 | 20.24 | 21.6 | 20.56 | 22.35 | 18 |
| Elastic modelling quantity (MPa) | 0.25 | 0.26 | 0.23 | 0.21 | 0.22 | 0.20 | 0.23 |
| Color | In vain | In vain | In vain | In vain | In vain | In vain | In vain |
| Fluorescence color | Blue | Yellowish green | Yellowish green | Yellowish green | Yellowish green | Yellowish green | Yellowish green |
| Long-persistence luminous illumination Lux | 1.2 | 1.07 | 1.29 | 1.62 | 1.68 | 1.97 | 2.06 |
Table 2. embodiment 1-7 coating real sea link plate result
Claims (8)
1. nano-antibacterial low surface energy organic silicon luminescence antifouling paint, it is characterised in that described coating includes the third component of the first component of 25～35 parts, the component B of 2～5 parts and 1 part by weight；
First component includes by weight:
Nano fluorescent predispersion 25.0～50.0 parts；
Organosilicon quaternary ammonium salt 5～25.0 parts；
Silicone oil 0.5～5.0 parts；
Component B includes by weight:
Crosslinking and curing agent 3.0～50.0 parts；
Silane coupler 1.0～10.0 parts；
Third component includes by weight:
Catalyst 0.1～3.0 parts；
Described catalyst is stannous octoate, dibutyltin diacetate, February
At least one in dilaurylate；
Described nano fluorescent predispersion is nano titanium oxide and fluorescent powder is dispersed in polyorganosiloxane resin by following weight portion；
Nano titanium oxide 2～5 parts；
Fluorescent powder 5～30 parts；
Polyorganosiloxane resin 50～70 parts；
Described nano fluorescent predispersion prepares by the following method: first polyorganosiloxane resin, solvent and dispersant is added in dispersion machine and is uniformly mixed, add nano titanium oxide high speed dispersion 30min under 4000～5000rpm, be subsequently adding fluorescent powder and continue high speed dispersion 15min；
The mixed method of described first component is: join in dispersion machine by each constituent of first component, with speed dispersed with stirring 30min of 1000～2000 revs/min, then stand-by after sand mill sand milling to fineness is less than 40 μm.
2. according to the coating described in claim 1, it is characterised in that described nano fluorescent predispersion also includes:
Solvent 5～15 parts；
Dispersant 0.5～1 part；
Described solvent is at least one in ketone, alcohols, aromatic hydrocarbon, esters.
3. according to the coating described in claim 1 or 2, it is characterised in that:
Described polyorganosiloxane resin is α, ω-polysiloxanediol, α, ω-dialkyl polydimethylsiloxane, α, at least one in ω-dihydroxy methyl silicone resins；
Described crosslinking and curing agent is methyl triacetoxysilane, at least one in silane containing alkoxyl, amino, amide groups, oximido or ketone group；
Described silane coupler be γ-aminopropyl triethoxysilane, γ-(2,3-glycidyl) propyl trimethoxy silicane,
At least one in N-(β-aminoethyl)-γ-aminopropyl trimethoxysilane, γ-(methacryloxypropyl) propyl trimethoxy silicane.
4. according to the coating described in claim 1, it is characterised in that described silicone oil is nonactive silicone oil.
5. according to the coating described in claim 1, it is characterised in that described organosilicon quaternary ammonium salt is quaternary ammonium salt cationic surfactant.
6. according to the coating described in claim 1 or 2, it is characterised in that described first component the most also includes:
White filler 1.0～25.0 parts
Auxiliary agent 0.5～5.0 parts
Described auxiliary agent is at least one in dispersant, defoamer, levelling agent, surfactant；
Described white filler is at least one in dicalcium powder, Pulvis Talci, barium sulfate, aluminium oxide, Kaolin, titanium white, zinc white.
7. according to the coating described in claim 1 or 2, it is characterised in that:
Described first component the most also includes:
Solvent 0.0～30.0 parts；
Described component B the most also includes:
Solvent 0.0～20.0 parts；
Described third component the most also includes:
Solvent 0.4～10.0 parts；
Described solvent is at least one in ketone, alcohols, aromatic hydrocarbon, esters.
8. the preparation method of the nano-antibacterial low surface energy organic silicon luminescence antifouling paint described in claim 1, it is characterised in that by described first, second, the third three components by described weight portion mix homogeneously, obtain after crosslinked solidification.
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| CN107474547A (en) * | 2017-09-12 | 2017-12-15 | 吉林大学 | Application of the elastomeric material in biodeterioration is prevented |
| CN107987722B (en) * | 2017-11-30 | 2019-11-05 | 深圳南玻应用技术有限公司 | Organosilicon bactericidal liquid, organosilicon fungicide, antibiotic glass, preparation method and application |
| CN108546437A (en) * | 2018-05-07 | 2018-09-18 | 中国科学院宁波材料技术与工程研究所 | A kind of antifouling paint, preparation method and application based on solid waste resource |
| CN110577798A (en) * | 2018-06-07 | 2019-12-17 | 中环海化(厦门)船舶智能涂料有限公司 | Energy-storage luminous self-cleaning water-based paint special for highway tunnel |
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| CN112940616A (en) * | 2021-03-26 | 2021-06-11 | 华南理工大学 | Hydrophobic antibacterial coating containing quaternary ammonium salt and preparation method and application thereof |
| CN113122034A (en) * | 2021-04-09 | 2021-07-16 | 柏桥生物科技有限公司 | Preparation method of antibacterial coating |
| CN113845838B (en) * | 2021-08-30 | 2022-04-05 | 盖科(浙江)生物科技有限公司 | Amphiphilic siloxane gel and preparation method thereof |
| CN114456707B (en) * | 2022-02-21 | 2023-04-07 | 浙江工业大学 | Quaternary ammonium salt antibacterial composite silicone rubber and synthesis method thereof |
| CN115505311B (en) * | 2022-10-27 | 2024-01-30 | 陕西世纪交通工程股份有限公司 | Environment-friendly self-luminous coating containing MMA resin and preparation method thereof |
| CN116496696B (en) * | 2023-05-08 | 2024-02-13 | 常熟理工学院 | Blending complexing mucous secretion-like marine antifouling paint and preparation method thereof |
| CN117247718A (en) * | 2023-10-08 | 2023-12-19 | 常熟理工学院 | Fouling release type marine antifouling paint based on intrinsic affinity |
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| CN101333349B (en) * | 2008-07-02 | 2010-11-17 | 大连海事大学 | Water-soluble luminous paint with long afterglow phosphorescent material coated by nanometer titanium dioxide and method for preparing same |
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