CN104327721A - Nano-antibacterial low-surface energy organosilicon luminescence anti-fouling paint and preparation method thereof - Google Patents
Nano-antibacterial low-surface energy organosilicon luminescence anti-fouling paint and preparation method thereof Download PDFInfo
- Publication number
- CN104327721A CN104327721A CN201410545977.1A CN201410545977A CN104327721A CN 104327721 A CN104327721 A CN 104327721A CN 201410545977 A CN201410545977 A CN 201410545977A CN 104327721 A CN104327721 A CN 104327721A
- Authority
- CN
- China
- Prior art keywords
- parts
- component
- nano
- weight
- dispersion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention discloses a nano-antibacterial low-surface energy organosilicon luminescence anti-fouling paint, which comprises the following components by weight: 25-35 parts of component A, 2-5 parts of component B and 1 part of component C; the component A comprises 25.0-50.0 parts of nano fluorescence pre-dispersion, 5-25.0 parts of organosilicon quaternary ammonium salt and 0.5-5.0 parts of silicone oil; the component B comprises 3.0-50.0 parts of crosslinking curing agent and 1.0-10.0 parts of silane coupling agent; The component C comprises 0.1-3.0 parts of catalyst; and the catalyst is at least one of stannous octoate, dibutyl tin diacetate and dibutyltin dilaurate. The paint has long persistence luminescent performance, has can prevent pollution by depending on fluorescence and enables contact sterilization, and has advantages of excellent antifouling performance, high strength and high adhesive force, can be used for various ships, sea petroleum platforms, marine structure and facility, marine aquaculture nets.
Description
Technical field
The invention belongs to luminous paint, staining-proof coating, antifouling paint, underwater coating compound technical field, be specifically related to luminous antifouling paint of nano-antibacterial low surface energy organic silicon and preparation method thereof.
Background technology
Halobiontic stained problem limits people to the development and utilization of marine resources always, the attachment of various marine life can cause ship resistance to increase, fuel consumption increases, the meta-bolites of marine life causes corrosion to ship, the maintenance cost of boats and ships can be increased, reduce ship in boat rate, marine life also can block the mesh of the various pipeline in seabed, valve and aquaculture net cage, the financial loss caused be difficult to estimation.In order to realize preventing and kill off halobiontic, application antifouling paint is the not only economy but also efficient important channel that the stained problem of solution is uniquely used widely.But, many antifouling paints of current use, contained by it, releasable antifouling toxic agent (as organotin, Red copper oxide) can cause Marine water to pollute, and causes biomutation, jeopardize marine food chain, to marine ecology balance and human health, there is potential hazard.Therefore, International Maritime Organizaton (IMO) the 21st session determines, the antifouling paint will thoroughly prohibitted the use containing organotin after on January 1st, 2008.For this situation, exploitation Wuxi, nontoxic environmental protection antifouling paint become the developing direction of antifouling paint.
Low surface energy anti-fouling paint to come off type antifouling paint also known as stained thing, coating is relied on to have low surface energy, can not only reduce and stop the attachment of various marine life, and environmentally friendly, toxicological harmless, significantly can reduce again the viscous friction drag of water, be the nontoxic anti-fouling anti-drag coated materials of the most promising a kind of boats and ships, receive extensive concern both domestic and external.Calculate according to international paint companies
[27]adopt low surface energy anti-fouling paint and the traditional poison of employing to expect compared with release type antifouling paint, boats and ships need the antifouling paint volume of application can reduce 80%, VOC noxious volatile gaseous emission minimizing 90%, the minimizing 100% of poison material, marine fuel oil consumption and the greenhouse gases (CO of equivalence
2) discharge minimizing 4-9%.The research and development of low surface energy anti-fouling paint relate generally to organosilicon and fluoropolymer two class.Organic silicon antifouling paint experienced by the R&D process from organo-silicone rubber to modified linear polysiloxane, and large quantifier elimination shows, although anti-fouling effect is not good, organic silicon antifouling paint demonstrates fouling organism removal effect more better than fluorine carbon antifouling paint.Therefore, study as product development, the attention of the international well-known paint company of organic silicon antifouling paint Geng Shou, in succession drops into the low surface energy anti-fouling paint that huge sum of money exploitation take polydimethylsiloxane as base-material, only has the only a few manufacturers such as Britain international standard paint company to have product to introduce to the market so far.Although low surface energy anti-fouling paint is still in the research and development stage, the application of low surface energy anti-fouling paint constantly expands, and has presented the trend progressively substituting self polishing copolymer antifouling paint, has represented the developing direction of antifouling paint.In a word, because organic silicon antifouling paint has huge application prospect, receive the concern of Chinese scholars, each large paint company all the time.
Although there have been some low surface energy anti-fouling paints to come into the market, antifouling for high-speed ship.But a large amount of real ship application shows, because boats and ships suspending time is longer, marine life still can be attached to hull bottom in a large number, needs periodic cleaning, and dirt settling, once grow up very difficult removing, thus makes its range of application be subject to certain restrictions.
Summary of the invention
For the problem of the active demand of domestic and international environmentally friendly marine antifouling anti-drag paint, the antifouling property deficiency of low surface energy anti-fouling paint existence, the invention provides the luminous antifouling paint of a kind of nano-antibacterial low surface energy organic silicon, this coating has long-persistence luminous performance, dependence fluorescence is antifouling, contact sterilization, have that antifouling property is excellent, intensity is high, sticking power advantages of higher, various boats and ships, offshore platform, marine structure and facility, mariculture netting gear etc. can be applied to.
Technical solution of the present invention is: the luminous antifouling paint of nano-antibacterial low surface energy organic silicon, comprises 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 comprises by weight:
Nano fluorescent predispersion 25.0 ~ 50.0 parts;
Organosilicon quaternary ammonium salt 5 ~ 25.0 parts;
Silicone oil 0.5 ~ 5.0 part;
Component B comprises by weight:
Crosslinking and curing agent 3.0 ~ 50.0 parts;
Silane coupling agent 1.0 ~ 10.0 parts;
Third component comprises by weight:
Catalyzer 0.1 ~ 3.0 part;
Described catalyzer is at least one in stannous octoate, dibutyltin diacetate, dibutyl tin dilaurate.
Described nano fluorescent predispersion is that nano titanium oxide and fluorescent powder are dispersed in polyorganosiloxane resin by following weight part;
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, is preferably 10-50nm.
The particle diameter of fluorescent powder is preferably 5 ~ 65 microns, is more preferably 25 ~ 40 microns.
Preferably, described nano fluorescent predispersion also comprises:
Solvent 5 ~ 15 parts;
Dispersion agent 0.5 ~ 1 part;
Described solvent is described solvent is at least one in ketone, alcohols, aromatic hydrocarbon, ester class.
Preferably, described polyorganosiloxane resin is α, alpha, omega-dihydroxy polysiloxane, α, alpha, omega-dihydroxy polydimethyl siloxane, α, at least one in alpha, omega-dihydroxy methyl silicone resins;
Described crosslinking and curing agent be tetraethoxy, methyl triacetoxysilane, containing at least one in the silane of alkoxyl group, amino, amide group, oximido or ketone group;
Described silane coupling agent is at least one in γ-aminopropyl triethoxysilane (KH550), γ-(2,3-epoxypropyl) propyl trimethoxy silicane (KH560), N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (KH792), γ-(methacryloxypropyl) propyl trimethoxy silicane (KH570).
Preferably, described silicone oil is described silicone oil is 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, and be a class quaternary ammonium salt cationic surfactant, its general structure is:
In formula, R is the group that can be hydrolyzed, as-OC
2h
5with-OCOOCl etc.; R
1for alkyl, containing oxygen or nitrogen-containing group, as-CH
2-,-CH
2cOCH
2cH
2-,-(CH
2)
3nCH
2cH
2-etc.; R
2for the alkyl containing 1 ~ 20 carbon atom; X is acid radical anion.
As preferred technical scheme, described first component also comprises by weight:
White filler 1.0 ~ 25.0 parts
Auxiliary agent 0.5 ~ 5.0 part
Described auxiliary agent is at least one in dispersion agent, defoamer, flow agent, tensio-active agent;
Described white filler is at least one in dicalcium powder, talcum powder, barium sulfate, aluminum oxide, kaolin, titanium white, zinc white.Described white filler is preferably the titanium dioxide of high covering power.
Wherein the available kind of auxiliary agent is respectively:
Dispersion agent: 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;
Flow agent: Bi Ke company BYK358, enlightening are high by 435, modest 435,433,837 at least one of moral.
As preferred technical scheme,
Described first component also comprises by weight:
Solvent 0.0 ~ 30.0 part;
Described component B also comprises by weight:
Solvent 0.0 ~ 20.0 part;
Described third component also comprises by weight:
Solvent 0.4 ~ 10.0 part;
Described solvent is at least one in ketone, alcohols, aromatic hydrocarbon, ester class.
Solvent of the present invention is preferably at least one in diacetylmethane, acetone, butanone, hexone, dehydrated alcohol, toluene, dimethylbenzene.
The present invention also provides the preparation method of the luminous antifouling paint of above-mentioned nano-antibacterial low surface energy organic silicon, described first, second, the third three components is mixed by described weight part, obtains after crosslinking curing.
Preferably, the blending means of described first component is: join in dispersion machine by each constituent of first component, with the 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.
Preferably, described nano fluorescent predispersion obtains by the following method: first polyorganosiloxane resin, solvent and dispersion agent are added in dispersion machine and be uniformly mixed, add nano titanium oxide high speed dispersion 30min under 4000 ~ 5000rpm again, then add fluorescent powder and continue high speed dispersion 15min.
The marine antifouling coating adopting technique scheme to make, can adopt the method constructions such as brushing, spraying or roller coating, stir evenly before using, can according to purposes and environment solvent adjustment viscosity.
Method of the present invention is a kind of method of synthesizing convenience, practicality, and involved basic raw material can commercially be buied very easily.
Marine antifouling coating of the present invention is applied to the soiling protective of boats and ships, marine structure, and having coatingsurface can be low, and marine life is not easy to attachment, even if attachment also easily self falling or the feature that is easily eliminated.And can be underwater facility, pipeline etc. and the effects such as mark, sign are provided.
The present invention is by scientifically designing the formula of organic silicon low-surface-energy antifouling paint, the content of the fillers such as the content of priority control organosilicon quaternary ammonium salt, nano titanium oxide, fluorescent powder, silicone oil etc. and titanium dioxide, coarse whiting, barium sulfate, the multiple collaborative antifouling object such as 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, low surface energy are antifouling; Nano titanium oxide, while the long-persistence luminous performance of raising coating, improves its intensity and antifraying property, and the surface topography of structure micro nano structure improves the anti-fouling anti-drag performance of coating further.Thus exploitation prepares novel nano antimicrobial organosilane low surface energy marine antifouling anti-drag paint, for marine green traffic provides technical support.
Beneficial effect of the present invention shows:
1. the present invention first prepares nano fluorescent predispersion by high speed shear dispersion, its favorable attributes outstanding behaviours, can the thoroughly nano titanium oxide of depolymerization secondary agglomeration and fluorescent powder, obtains nano titanium oxide and the nano fluorescent predispersion of fluorescent powder full and uniform dispersion in polyorganosiloxane resin.Nano titanium oxide and fluorescent powder are evenly blended, have the synergism improving the long-persistence luminous performance of fluorescent powder, strengthen the fluorescence antifouling property of coating, have significant anti-fouling effect to marine animal (particularly barnacle) larva of detesting light.
2. the silane coupling agent contained in antifouling paint of the present invention, for coating of the present invention provides the bonding force excellent with ground, coating of the present invention directly can be coated with and be contained 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 of saving boats and ships.
3. the small molecules silicone oil containing a certain amount of reactionless activity in antifouling paint of the present invention, in military service process after paint solidification, due to the effect of interfacial tension, it migration can be discharged into the activated interface of coating and seawater gradually, form the silicon oil membrane of the soft stick-slip instability of one deck, reduce the attachment of marine life at hull surface on the one hand, greatly can weaken the bonding force of attachment marine life and hull coatings on the other hand, make attachment marine life be easy to self falling under the souring of seawater, there is excellent anti-fouling anti-drag performance.
4. antifouling paint smooth surface of the present invention, has the effect reducing ship resistance, reduce marine fuel oil consumption and greenhouse gas emission.
5. antifouling paint of the present invention contains a certain amount of nano titanium oxide, makes coating not only have excellent photo-catalyst antifouling property, and has excellent mechanical property and higher hardness, ensures that coating has higher wear-resistant and anti-scuffing function.
6. antifouling paint of the present invention contains a certain amount of organosilyl quaternary ammonium salt sterilizing agent, after itself and silicone resin crosslinking curing, be uniformly distributed in the coating with the form of segment, when with the marine organisms larva of negatively charged ion or spore near coatingsurface time, the quaternary ammonium salt cationic of coatingsurface and marine organisms cell with anion binding, cause cell to be destroyed, play the object that contact sterilization is antifouling, and objectionable impurities can not be discharged in ocean environment.
Embodiment
The present invention will be described to enumerate embodiment below, but the present invention is not by the restriction of following embodiment, and can make various changes in the scope meeting aim before and after the present invention, these are all included in 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 silicon rubber, viscosity (25 DEG C): 2500 ~ 1000000mPas, the α of different viscosity can be selected as required, alpha, omega-dihydroxy polydimethyl siloxane, the mainly viscosity used in the embodiment of the present invention is respectively the α of 2800mPas and 10000mPas, alpha, omega-dihydroxy polydimethyl siloxane, but implement the present invention and selected polyorganosiloxane resin, be not limited to producer and specific performance parameter thereof.
Silicate luminescent material (blue colour fluorescent powder SB-8C), alkaline earth aluminates phosphors (yellowish green fluorescent powder PLO-7C), alkaline-earth aluminosilicate luminescent material (yellowish green fluorescent powder SP-4) that the fluorescent powder that described invention is selected is produced purchased from MingFa optical Science Co., Ltd., DaLian Road.But implement the present invention and selected fluorescent powder, be not limited to producer and specific performance parameter thereof.
The organosilicon quaternary ammonium salt that the organosilicon quaternary ammonium salt that described invention is selected is produced purchased from Guangzhou Nuokang Chemical Co., Ltd., particular chemical [(CH
3cH
2o)
3si (CH
2)
3n
+(CH
3)
2c
18h
37] Cl
-.But implement the present invention and selected organosilicon quaternary ammonium salt, be not limited to producer and specific performance parameter thereof.
The nano titanium oxide that described invention is selected be purchased from Beyer Co., Ltd sell P25 mixed crystal type nanometer titanium dioxide, the work production and sales of abundant Xinghua, Jinan nanometer anatase titania.The titanium dioxide that the present invention selects is not limited to producer and specific performance parameter thereof, optional with having the anatase titanium dioxide of photocatalytic effect, rutile-type or mixed crystal type nanometer titanium dioxide.
Embodiment 1
In proportion first by the α of 70 parts of viscosity 10000mPas, alpha, omega-dihydroxy polydimethyl siloxane, 1 part of dispersant B YK161,10 parts of dimethylbenzene and 3 parts of domestic nanometer anatase titanias add in the dispersion tank of dispersion machine, high speed dispersion 30min under 4000rpm, then add 16 parts of blue colour fluorescent powder SB-8C and continue high speed dispersion 15min, obtained nano fluorescent predispersion.
Each constituent joins in the dispersion tank of dispersion machine by first component in proportion successively, with the speed high-speed stirring of 2000 revs/min dispersion 30min, then canned stand-by after sand mill sand milling to fineness is less than 40 μm.
Component B and the third component mix rear canned stand-by respectively according to proportioning.
According to first before using: the ratio mixing and stirring of second: third=30:4:1, after application, solidification, obtain organosilicon low surface energy antifouling coating.
First component forms:
Component B forms:
Tetraethoxy 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
Diacetylmethane 9.0 parts
Embodiment 2
In proportion first by the α of 60 parts of viscosity 10000mPas, alpha, omega-dihydroxy polydimethyl siloxane, 1 part of dispersant B YK161,8 parts of dimethylbenzene and 2 parts of domestic nanometer anatase titanias add in the dispersion tank of dispersion machine, high speed dispersion 30min under 4000rpm, then add 10 parts of yellowish green fluorescent powder SP-4 and continue high speed dispersion 15min, obtained nano fluorescent predispersion.
Each constituent joins in the dispersion tank of dispersion machine by first component in proportion successively, with the speed high-speed stirring of 1500 revs/min dispersion 30min, then canned stand-by after sand mill sand milling to fineness is less than 40 μm.
Component B and the third component mix rear canned stand-by respectively according to proportioning.
According to first before using: the ratio mixing and stirring of second: third=25:4:1, after application, solidification, obtain organosilicon low surface energy antifouling coating.
First component forms:
Component B forms:
Tetraethoxy 5.0 parts
Silane coupling agent KH560 3.0 parts
Dehydrated alcohol 11.0 parts
Third component composition:
Dibutyl tin laurate 3.0 parts
7.0 parts, acetone
Embodiment 3
In proportion first by the α of 50 parts of viscosity 10000mPas, the α of alpha, omega-dihydroxy polydimethyl siloxane, 20 parts of viscosity 2800mPas, alpha, omega-dihydroxy polydimethyl siloxane, 1 part of dispersant B YK161,10 parts of dimethylbenzene and 3 parts of domestic nanometer anatase titanias add in the dispersion tank of dispersion machine, high speed dispersion 30min under 4500rpm, then add 16 parts of yellowish green fluorescent powder SP-4 and continue high speed dispersion 15min, obtained nano fluorescent predispersion.
Each constituent joins in the dispersion tank of dispersion machine by first component in proportion successively, with the speed high-speed stirring of 1800 revs/min dispersion 30min, then canned stand-by after sand mill sand milling to fineness is less than 40 μm.
Component B and the third component mix rear canned stand-by respectively according to proportioning.
According to first before using: the ratio mixing and stirring of second: third=35:5:1, after application, solidification, obtain organosilicon low surface energy antifouling coating.
First component forms:
Component B forms:
Tetraethoxy 5.0 parts
Silane coupling agent KH560 3.0 parts
Dehydrated alcohol 11.0 parts
Third component composition:
Dibutyl tin laurate 3.0 parts
Diacetylmethane 7.0 parts
Embodiment 4
In proportion first by the α of 55 parts of viscosity 10000mPas, alpha, omega-dihydroxy polydimethyl siloxane, 0.5 part of dispersant B YK163,5 parts of dimethylbenzene and 4 parts of import P25 nano titanium oxides add in the dispersion tank of dispersion machine, high speed dispersion 30min under 4000rpm, then add 18 parts of yellowish green fluorescent powder SP-4 and continue high speed dispersion 15min, obtained nano fluorescent predispersion;
Each constituent joins in the dispersion tank of dispersion machine by first component in proportion successively, with the speed high-speed stirring of 1200 revs/min dispersion 30min, then canned stand-by after sand mill sand milling to fineness is less than 40 μm.
Component B and the third component mix rear canned stand-by respectively according to proportioning.
According to first before using: the ratio mixing and stirring of second: third=25:2:1, after application, solidification, obtain organosilicon low surface energy antifouling coating.
First component forms:
Component B forms:
Tetraethoxy 5.0 parts
Silane coupling agent KH570 3.0 parts
11.0 parts, acetone
Third component composition:
Dibutyl tin laurate 3.0 parts
Dimethylbenzene 7.0 parts
Embodiment 5
In proportion first by the α of 65 parts of viscosity 10000mPas, alpha, omega-dihydroxy polydimethyl siloxane, 0.8 part of dispersant B YK161,10 parts of dimethylbenzene and 3 parts of import P25 nano titanium oxides add in the dispersion tank of dispersion machine, high speed dispersion 30min under 4000rpm, then add 30 parts of yellowish green fluorescent powder PLO-7C and continue high speed dispersion 15min, obtained nano fluorescent predispersion.
Each constituent joins in the dispersion tank of dispersion machine by first component in proportion successively, with the speed high-speed stirring of 1500 revs/min dispersion 30min, then canned stand-by after sand mill sand milling to fineness is less than 40 μm.
Component B and the third component mix rear canned stand-by respectively according to proportioning.
According to first before using: the ratio mixing and stirring of second: third=30:4:1, after application, solidification, obtain organosilicon low surface energy antifouling coating.
First component forms:
Component B forms:
Tetraethoxy 5.0 parts
Silane coupling agent KH792 3.0 parts
Dimethylbenzene 11.0 parts
Third component composition:
Dibutyl tin laurate 3.0 parts
Diacetylmethane 7.0 parts
Embodiment 6
In proportion first by the α of 50 parts of viscosity 10000mPas, the α of alpha, omega-dihydroxy polydimethyl siloxane, 30 parts of viscosity 2800mPas, alpha, omega-dihydroxy polydimethyl siloxane, 1 part of dispersant B YK161,5 parts of dimethylbenzene and 4 parts of import P25 nano titanium oxides add 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, obtained nano fluorescent predispersion.
Each constituent joins in the dispersion tank of dispersion machine by first component in proportion successively, with the speed high-speed stirring of 3500 revs/min dispersion 30min, then canned stand-by after sand mill sand milling to fineness is less than 40 μm.
Component B and the third component mix rear canned stand-by respectively according to proportioning.
According to first before using: the ratio mixing and stirring of second: third=28:3:1, after application, solidification, obtain organosilicon low surface energy antifouling coating.
First component forms:
Component B forms:
Tetraethoxy 5.0 parts
Silane coupling agent KH792 3.0 parts
Dehydrated alcohol 11.0 parts
Third component composition:
Dibutyl tin laurate 2.0 parts
Diacetylmethane 8.0 parts
Embodiment 7
In proportion first by the α of 20 parts of viscosity 10000mPas, the α of alpha, omega-dihydroxy polydimethyl siloxane, 30 parts of viscosity 2800mPas, alpha, omega-dihydroxy polydimethyl siloxane, 1 part of dispersant B YK161,5 parts of dimethylbenzene and 5 parts of import P25 nano titanium oxides add 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, obtained nano fluorescent predispersion.
Each constituent joins in the dispersion tank of dispersion machine by first component in proportion successively, with the speed high-speed stirring of 5000 revs/min dispersion 30min, then canned stand-by after sand mill sand milling to fineness is less than 40 μm.
Component B and the third component mix rear canned stand-by respectively according to proportioning.
According to first before using: the ratio mixing and stirring of second: third=28:4:1, after application, solidification, obtain organosilicon low surface energy antifouling coating.
First component forms:
Component B forms:
Tetraethoxy 5.0 parts
Silane coupling agent KH792 3.0 parts
Dimethylbenzene 11.0 parts
Third component composition:
Dibutyl tin laurate 3.0 parts
Diacetylmethane 7.0 parts
Coating property measuring method and result
Measure the surface water contact angle of coating model, methylene iodide contact angle, surface free energy, Young's modulus, shore hardness and antifouling property, measuring method is as follows, and measurement result is as shown in table 1.
1. contact angle
The contact angle on the JC2000 type contact angle instrument testing coating surface adopting Shanghai Zhongchen digital technology equipment Co., Ltd to produce.2 μ l deionized waters or methylene iodide are connect to drip and test after 10 seconds in coatingsurface, 3 points that distance 5mm mutually got by each coating model are taken pictures, and then adopt goniometry to measure left and right contact angle respectively, totally 6 readings, average as measured value.
2. surface energy estimation
Measure water contact angle and the methylene iodide contact angle of film respectively, after obtaining mean value, substitute into following formula gauging surface energy:
Wherein,
be respectively water contact angle and the methylene iodide contact angle of this coating.
3. Young's modulus
In order to measure the Young's modulus of coating, Teflon mould injection molding is utilized to obtain long 120mm, wide 60mm, thick 2mm sample, cut into tension specimen (long 50mm, wide 15mm, thick 2mm), use blue streak dynamo-electric factory in Jinan to produce the stress strain curve of XLW type electronics tension tester mensuration coating, calculating elastic modulus, rate of extension is 25mm/min.The thickness of the front typing sample of stretching and width, thickness adopts the average of vernier caliper measurement testing bar two ends and mid-way thickness, calculates its cross-sectional area, and record tension specimen data, can obtain the Young's modulus of sample by analyzing this curve.Each coating tests 3 times, averages.
Young's modulus is stress-strain(ed) curve slope, its method of calculation as shown in the formula, unit is MPa.
Wherein, b, d are the initial width of sample and thickness, L
0for the initial length of sample stretch zones, the length of stretch zones when L is stressed F.
4. shore hardness
The shore hardness of coating is measured with HT220 Shore A durometer.Concrete grammar is: by folding for injection molded specimens to ensure that sclerometer probe does not affect by other body surface hardness except injection molded specimens as far as possible, take three different positionss measure and get its mean value.
5. antifouling property test
Carry out link plate preparation and Dalian Sea Area shallow sea board experiment according to standard GB/T 5370-85 antifouling varnish model shallow sea soak test method, evaluate the antifouling property of coating.Test is carried out in Port Arthur floating terminal, and on model framework, edge and lower edge are dipped in respectively apart from the seawater of sea level 0.5m to 2m.Carry out link plate every month and observe inspection, test and appraisal biological attachment 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 is about 10cm, after jet of water rinses the settled organism of specimen surface, evaluates the condition of surface of fouling release complexity and the rear coating of removing.
6. coating color
The color of coating and fluorescence color visual evaluation.
7. long-persistence luminous illumination
To the tinplate of 50 micron thickness coatings of having an appointment be coated with at fixed light source (fluorescent lamp intensity of illumination 133.5Lux during experiment, plate identity distance fluorescent tube height is 55.5cm) under illumination 5min, then fluorescent lamp is closed, the ST-900 type faint light photometer/radiometer measurement intensity of illumination adopting Aobodi Photoelectric Technology Co., Ltd., Beijing to produce immediately in dark conditions, lists in instrument readings in table 1 as measuring 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 |
| Methylene iodide contact angle (°) | 72.92 | 79 | 75.08 | 72.75 | 75.42 | 72.08 | 79.08 |
| Surface energy (mJ/m 2) | 21.91 | 18.08 | 20.24 | 21.6 | 20.56 | 22.35 | 18 |
| Young's modulus (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 |
The real extra large link plate result of table 2. embodiment 1-7 coating
Claims (10)
1. the luminous antifouling paint of nano-antibacterial low surface energy organic silicon, is characterized in that, described coating comprises 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 comprises by weight:
Nano fluorescent predispersion 25.0 ~ 50.0 parts;
Organosilicon quaternary ammonium salt 5 ~ 25.0 parts;
Silicone oil 0.5 ~ 5.0 part;
Component B comprises by weight:
Crosslinking and curing agent 3.0 ~ 50.0 parts;
Silane coupling agent 1.0 ~ 10.0 parts;
Third component comprises by weight:
Catalyzer 0.1 ~ 3.0 part;
Described catalyzer is at least one in stannous octoate, dibutyltin diacetate, dibutyl tin dilaurate;
Described nano fluorescent predispersion is that nano titanium oxide and fluorescent powder are dispersed in polyorganosiloxane resin by following weight part;
Nano titanium oxide 2 ~ 5 parts;
Fluorescent powder 5 ~ 30 parts;
Polyorganosiloxane resin 50 ~ 70 parts.
2. coating according to claim 1, is characterized in that, described nano fluorescent predispersion also comprises:
Solvent 5 ~ 15 parts;
Dispersion agent 0.5 ~ 1 part;
Described solvent is described solvent is at least one in ketone, alcohols, aromatic hydrocarbon, ester class.
3. coating according to claim 1 and 2, is characterized in that:
Described polyorganosiloxane resin is α, alpha, omega-dihydroxy polysiloxane, α, alpha, omega-dihydroxy polydimethyl siloxane, α, at least one in alpha, omega-dihydroxy methyl silicone resins;
Described crosslinking and curing agent be tetraethoxy, methyl triacetoxysilane, containing at least one in the silane of alkoxyl group, amino, amide group, oximido or ketone group;
Described silane coupling agent is at least one in γ-aminopropyl triethoxysilane, γ-(2,3-epoxypropyl) propyl trimethoxy silicane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-(methacryloxypropyl) propyl trimethoxy silicane.
4. coating according to claim 1, is characterized in that, described silicone oil is nonactive silicone oil.
5. coating according to claim 1, is characterized in that, described organosilicon quaternary ammonium salt is quaternary ammonium salt cationic surfactant.
6. coating according to claim 1 and 2, is characterized in that, described first component also comprises by weight:
White filler 1.0 ~ 25.0 parts
Auxiliary agent 0.5 ~ 5.0 part
Described auxiliary agent is at least one in dispersion agent, defoamer, flow agent, tensio-active agent;
Described white filler is at least one in dicalcium powder, talcum powder, barium sulfate, aluminum oxide, kaolin, titanium white, zinc white.
7. coating according to claim 1 and 2, is characterized in that:
Described first component also comprises by weight:
Solvent 0.0 ~ 30.0 part;
Described component B also comprises by weight:
Solvent 0.0 ~ 20.0 part;
Described third component also comprises by weight:
Solvent 0.4 ~ 10.0 part;
Described solvent is at least one in ketone, alcohols, aromatic hydrocarbon, ester class.
8. the preparation method of the luminous antifouling paint of nano-antibacterial low surface energy organic silicon described in claim 1-7 any one, is characterized in that, described first, second, the third three components is mixed by described weight part, obtains after crosslinking curing.
9. preparation method according to claim 8, it is characterized in that, the blending means of described first component is: join in dispersion machine by each constituent of first component, with the 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.
10. preparation method according to claim 9, it is characterized in that, described nano fluorescent predispersion obtains by the following method: first polyorganosiloxane resin, solvent and dispersion agent are added in dispersion machine and be uniformly mixed, add nano titanium oxide high speed dispersion 30min under 4000 ~ 5000rpm again, then add fluorescent powder and continue high speed dispersion 15min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410545977.1A CN104327721B (en) | 2014-10-15 | 2014-10-15 | Nano-antibacterial low surface energy organic silicon luminescence antifouling paint and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410545977.1A CN104327721B (en) | 2014-10-15 | 2014-10-15 | Nano-antibacterial low surface energy organic silicon luminescence antifouling paint and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104327721A true CN104327721A (en) | 2015-02-04 |
| CN104327721B CN104327721B (en) | 2016-12-07 |
Family
ID=52402535
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410545977.1A Active CN104327721B (en) | 2014-10-15 | 2014-10-15 | Nano-antibacterial low surface energy organic silicon luminescence antifouling paint and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104327721B (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153889A (en) * | 2015-07-30 | 2015-12-16 | 安徽荣达阀门有限公司 | Fireproof flame-retardation type valve antifouling powdery paint and manufacturing method thereof |
| CN107474547A (en) * | 2017-09-12 | 2017-12-15 | 吉林大学 | Application of the elastomeric material in biodeterioration is prevented |
| 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 |
| WO2019105068A1 (en) * | 2017-11-30 | 2019-06-06 | 深圳南玻应用技术有限公司 | Organosilicon antimicrobial solution, organosilicon antimicrobial agent, antimicrobial glass, preparation method therefor and use thereof |
| 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 |
| CN110885590A (en) * | 2019-10-18 | 2020-03-17 | 华艺生态园林股份有限公司 | Durable anti-dropping multifunctional tree color pigment |
| 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 |
| CN113845838A (en) * | 2021-08-30 | 2021-12-28 | 盖科(浙江)生物科技有限公司 | Amphiphilic siloxane gel and preparation method thereof |
| CN114456707A (en) * | 2022-02-21 | 2022-05-10 | 浙江工业大学 | Quaternary ammonium salt antibacterial composite silicone rubber and synthesis method thereof |
| CN115505311A (en) * | 2022-10-27 | 2022-12-23 | 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 |
| CN116496696A (en) * | 2023-05-08 | 2023-07-28 | 常熟理工学院 | Blending complexing mucous secretion-like marine antifouling paint and preparation method thereof |
| CN116656213A (en) * | 2023-06-27 | 2023-08-29 | 厦门双瑞船舶涂料有限公司 | Self-lubricating fouling self-stripping type anti-fouling 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1810910A (en) * | 2006-02-28 | 2006-08-02 | 成都硅宝科技实业有限责任公司 | Anti-fouling single-component room temperature sealing silicone sulfide glue and its production process |
| CN101333349A (en) * | 2008-07-02 | 2008-12-31 | 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 |
| US20090221752A1 (en) * | 2006-03-06 | 2009-09-03 | Jotun As | Fouling release composition |
| CN103965827A (en) * | 2014-05-04 | 2014-08-06 | 天津航瑞丰源科技有限公司 | Super-hydrophobic and anti-pollution flashover one-component adhesive, and preparation method and application thereof |
-
2014
- 2014-10-15 CN CN201410545977.1A patent/CN104327721B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1810910A (en) * | 2006-02-28 | 2006-08-02 | 成都硅宝科技实业有限责任公司 | Anti-fouling single-component room temperature sealing silicone sulfide glue and its production process |
| US20090221752A1 (en) * | 2006-03-06 | 2009-09-03 | Jotun As | Fouling release composition |
| CN101333349A (en) * | 2008-07-02 | 2008-12-31 | 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 |
| CN103965827A (en) * | 2014-05-04 | 2014-08-06 | 天津航瑞丰源科技有限公司 | Super-hydrophobic and anti-pollution flashover one-component adhesive, and preparation method and application thereof |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153889A (en) * | 2015-07-30 | 2015-12-16 | 安徽荣达阀门有限公司 | Fireproof flame-retardation type valve antifouling powdery paint and manufacturing method thereof |
| CN107474547A (en) * | 2017-09-12 | 2017-12-15 | 吉林大学 | Application of the elastomeric material in biodeterioration is prevented |
| US11219217B2 (en) | 2017-11-30 | 2022-01-11 | Shenzhen Csg Applied Technology Co., Ltd | Organosilicon antimicrobial solution, organosilicon antimicrobial agent, antimicrobial glass, preparation method therefor and use thereof |
| WO2019105068A1 (en) * | 2017-11-30 | 2019-06-06 | 深圳南玻应用技术有限公司 | Organosilicon antimicrobial solution, organosilicon antimicrobial agent, antimicrobial glass, preparation method therefor and use thereof |
| JP2021504300A (en) * | 2017-11-30 | 2021-02-15 | 深▲セン▼南玻應用技術有限公司Ｓｈｅｎｚｈｅｎ Ｃｓｇ Ａｐｐｌｉｅｄ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏ．， Ｌｔｄ | Organosilicon antibacterial solution, organosilicon antibacterial agent, antibacterial glass, manufacturing method for it and its use |
| JP6997308B2 (en) | 2017-11-30 | 2022-01-17 | 深▲せん▼南玻應用技術有限公司 | Organosilicon antibacterial solution, organosilicon antibacterial agent, antibacterial glass, manufacturing method for it and its use |
| 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 |
| CN110885590A (en) * | 2019-10-18 | 2020-03-17 | 华艺生态园林股份有限公司 | Durable anti-dropping multifunctional tree color pigment |
| 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 |
| CN113845838A (en) * | 2021-08-30 | 2021-12-28 | 盖科(浙江)生物科技有限公司 | Amphiphilic siloxane gel and preparation method thereof |
| 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 |
| CN114456707A (en) * | 2022-02-21 | 2022-05-10 | 浙江工业大学 | Quaternary ammonium salt antibacterial composite silicone rubber and synthesis method thereof |
| CN115505311A (en) * | 2022-10-27 | 2022-12-23 | 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 |
| 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 |
| CN116496696A (en) * | 2023-05-08 | 2023-07-28 | 常熟理工学院 | Blending complexing mucous secretion-like marine antifouling paint 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 |
| CN116656213A (en) * | 2023-06-27 | 2023-08-29 | 厦门双瑞船舶涂料有限公司 | Self-lubricating fouling self-stripping type anti-fouling 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104327721B (en) | 2016-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104327721B (en) | Nano-antibacterial low surface energy organic silicon luminescence antifouling paint and preparation method thereof | |
| CN104231919B (en) | Nanometer reinforced, non-transition-layer, organosilicone and low-surface-energy type antifouling paint and preparation method thereof | |
| ES2856685T3 (en) | Antifouling Coating Composition, Antifouling Coating Film, Antifouling Substrate and Method for Improving the Storage Stability of the Antifouling Coating Composition | |
| CN104231920B (en) | Organic silicon middle connecting coating and preparation method thereof | |
| JP4195537B2 (en) | Curable composition, coating composition, paint, antifouling paint, cured product thereof, and substrate antifouling method | |
| CN101440256B (en) | Antifouling condensation curing organopolysiloxane composition, making method, and underwater structure | |
| DE602004008793T2 (en) | HAFTSCHICHTMASSE WITH AT LEAST TWO PIECES OF FUNCTIONAL POLYSILOXAN COMPOUNDS AND CORRESPONDING USE | |
| CN101679786B (en) | Anti-fouling coating compositions containing a carboxyl-functional organosilicone | |
| DE60207398T2 (en) | Antifungal compositions containing fluorinated alkynyl or alkoxy-substituted polymer or oligoomer | |
| JP2007016096A (en) | Curable composition, composition for coating, coating material, antifouling coating material, cured product thereof and antifouling method of base material | |
| JPWO2008081789A1 (en) | Curable composition, antifouling coating composition, antifouling coating film, substrate with antifouling coating, and method for antifouling substrate | |
| JP6431549B2 (en) | Method for reinforcing antifouling coating | |
| JP6847128B2 (en) | Antifouling paint composition, antifouling coating film, base material with antifouling coating film and its manufacturing method, and antifouling method | |
| JP2001181509A (en) | Curable composition, coating composition, coating material, antifouling coating material, its cured product, and antifouling method of substrate | |
| JP6309626B2 (en) | Antifouling paint composition | |
| CN106366882B (en) | A kind of flexible self polishing copolymer antifouling paint and preparation method thereof with anti-drag function | |
| WO2020071537A1 (en) | Antifouling coating composition, antifouling coating film, substrate with antifouling coating film and method for producing same | |
| CN108329831A (en) | A kind of antifouling low-surface-energy polysiloxane composition and application | |
| JP2017088653A (en) | Coating composition, antifouling coated film, antifouling substrate and manufacturing method of antifouling substrate | |
| EP3077468A2 (en) | A method for coating an aged coating layer on a substrate, and a coating composition suitable for use in this method | |
| CN108559394A (en) | A kind of bi-component organic silicon antifouling paint and preparation method thereof | |
| CN108148501A (en) | Organosilicon anti-drag paint composition and application | |
| JP6487159B2 (en) | Antifouling paint composition, antifouling film, method for producing antifouling film and antifouling substrate | |
| CN114479661A (en) | Low-surface-energy anti-drag antifouling paint and preparation method thereof | |
| CN110951333A (en) | Environment-friendly antifouling paint |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |