CN107556856A - A kind of nano-antibacterial antifouling paint - Google Patents
A kind of nano-antibacterial antifouling paint Download PDFInfo
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- CN107556856A CN107556856A CN201610475046.8A CN201610475046A CN107556856A CN 107556856 A CN107556856 A CN 107556856A CN 201610475046 A CN201610475046 A CN 201610475046A CN 107556856 A CN107556856 A CN 107556856A
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Abstract
The present invention relates to paint field, particularly a kind of nano-antibacterial antifouling paint, the coating is mainly used in the antifouling of ship.By mass percentage, component one includes：Organosilicon modified crylic acid resin 20%~60%, polydimethylsiloxaneresins resins 0.5%~10%, silicon fluoride modified Nano SiO20.5%~10%, constitution color stuffing 20%~40%, auxiliary agent account for 5%~15%, organic solvent 10%~30%.1) nanosized SiO_2 is subjected to silicon fluoride surface treatment；2) the silicon fluoride modified Nano SiO2 after processing is prepared into thickened pulp；3) silicon fluoride modified Nano SiO2 thickened pulps and other raw materials are mixed, antifouling paint component one is prepared.Curing agent is dissolved to obtain component two, and component one is added in component two, is solidified 30min~15 day at 10~30 DEG C, is formed low surface energy nano polyurethane anti-fouling paint.Antifouling paint involved in the present invention utilizes the new technology of nano-particle processing, has surface energy low, the problem of release in the absence of poisonous substance, and safety and environmental protection.
Description
The present invention relates to paint field, particularly a kind of nano-antibacterial antifouling paint.
Being stained of marine organisms is defined as microorganism, the thalassophyte and animal undesirably labor statement in ocean
The accumulation in face.The position of hull underwater is soaked by seawater for a long time, is easily stained a variety of sea hydrobionts, such as barnacle, mussel, pipe
Worm and marine alga etc..The biodeterioration of hull surface can produce high frictional resistance, increase hull weight, reduce the traveling speed of ship
Degree, ultimately results in increase fuel consumption.Except increasing fuel consumption, biodeterioration can increase the frequency that ship enters dock repair, lead
Cause Ship's corrosion.
The marime fouling of hull all the time, is controlled by adding organo-tin compound or cuprous oxide in topside paint
System, these compounds have the function of being released slowly into water body environment.This approach effectively control biodeterioration while,
Bring the worry of serious environmental problem.In fact, International Maritime Organization has prohibitted the use of the coating containing organotin, oxidation
Cuprous class can also be used in the future by control.So the shipping business in the whole world is required for the friendly topside paint of use environment at present
To control marine biofouling.Low surface energy anti-fouling paint reaches antifouling mesh based on the coating surface for creating low-surface-energy
, without using or use anti-fouling agent less, so as to reach the target of asepsis environment-protecting.
It is an object of the invention to provide a kind of nano-antibacterial antifouling paint, problem to be solved is to utilize resins synthesis
Technology, nanoparticle surface treatment technology and nano slurry technology of preparing, it is good to develop a kind of nontoxic, low-surface-energy, stability, and
Has the Nano-meter SiO_2 of good workability2/ polyurethane antifouling paint, this antifouling paint is except for marine antifouling, it can also be used to
Other occasions using hydrophobic coating.
The technical scheme is that：
A kind of low surface energy nano polyurethane anti-fouling paint, coating are made up of following two parts：
By mass percentage, component one is formulated by following component and quality proportioning：
By mass percentage, component two is formulated by following component and quality proportioning：
Organic solvent 25~100% (being preferably 50~80%)；
Curing agent 0~75% (being preferably 20~50%)；
Count in mass ratio, component one: component two=2~10: 1 mixes, and obtains low-surface-energy nano antifouling coating.
The component of the organosilicon modified crylic acid resin is as follows：
The silicon fluoride modified Nano SiO2For Nano-meter SiO_22Surface grafting silicon fluoride, Nano-meter SiO_22Average grain diameter is in 100nm
Hereinafter, wherein silicon fluoride: Nano-meter SiO_22Mass ratio is 0.05~0.3: 1.In the present invention, silicon fluoride refers to 17 fluorine decyl front threes
TMOS, trifluoro propyl methyl dimethoxysilane, trifluoro propyl trimethoxy silane, (N- perfluorooctyl sulfonyls)-ammonia
Propyl-triethoxysilicane, tridecafluoro-n-octyltriethoxysilane, trifluoro propyl methyl cyclotrisiloxane, the ethoxy of trifluoro propyl three
One of base silane etc..
Described constitution color stuffing is titanium dioxide, calcium carbonate, zinc oxide, graphite, iron oxide red, carbon black, talcum powder, precipitation
The one or more of barium sulfate and organic pigment, the granularity of constitution color stuffing is micron order.
The auxiliary agent is the auxiliary agent being commonly used in dope preparing process, including dispersant, levelling agent and anti-settling agent.Such as：
The BYK series auxiliary agents of German Bi Ke chemical companies；Dispersant, such as：BYK101 dispersants, BYK104 dispersants, BYK110 disperse
Agent, BYK130 dispersants, BYK141 dispersants or BYK161 dispersants etc.；Levelling agent, such as：BYK 358N levelling agents, BYK300
Levelling agent, BYK306 levelling agents, BYK307 levelling agents, BYK310 levelling agents or BYK320 levelling agents etc.；Anti-settling agent, such as：
BYK410 anti-settling agents, BYK420 anti-settling agents, BYK431 anti-settling agents or BYK411 anti-settling agents etc..
Described organic solvent is aromatic hydrocarbon or esters, and described aromatic hydrocarbon is that benzene, toluene and dimethylbenzene are a kind of or a kind of
More than, described esters are that ethyl acetate, n-butyl acetate and isobutyl acetate are one or more kinds of.
Described curing agent is Isocyanates curing agent, such as：The MR100 of Jiangyin mole new chemical materialses Co., Ltd,
The isocyanate curing agents such as MR200, MR310 or MR330.Or Beyer Co., Ltd L75, L50, N75, N3390, HL, VL or
3790 grade isocyanate curing agents.
The preparation method of described low surface energy nano polyurethane anti-fouling paint, comprises the following steps：
1) using organosilicon modified crylic acid resin as matrix, silicon fluoride modified Nano SiO is added2Thickened pulp, add
Constitution color stuffing, organic solvent, auxiliary agent, it is scattered 10~30 minutes with 800~1500rpm of high speed centrifugation dispersion machine；
2) polydimethylsiloxaneresins resins are added, are continued scattered 10~30 points with 800~1500rpm of high speed centrifugation dispersion machine
Clock；Then reach less than 40 μm to fineness within 4~8 hours with ball mill grinding, discharging, obtain component one；
3) curing agent is added in organic solvent, curing agent is dissolved in organic solvent, obtain component two；
4) component one is added in component two, solidifies 30min~15 day at 10~30 DEG C, formed low-surface-energy nanometer and gather
Urethane antifouling paint.
In the present invention, by mass percentage, preparing the raw material composition of organosilicon modified crylic acid resin is：Metering system
Sour methyl esters 15%~40%, n-butyl acrylate 5%~20%, isobornyl methacrylate 10%~30%, acrylic acid hydroxyl
Ethyl ester 5%~15%；Organic silicon monomer 5%~15%, toluene 5%~20%, azodiisobutyronitrile 0.1%~0.5%, methyl
Isobutyl ketone 20%~50%.
First, organic solvent is mixed with initiator azodiisobutyronitrile, is heated to 60-80 DEG C, rocked, it is equal to mixing
It is even, form mixed solution A；Equipped with agitating device, condenser, thermometer, dropping funel four round flask in add first
Benzene and hexone, it is warming up to 50~90 DEG C；Organic silicon monomer, methyl methacrylate, acrylic acid are uniformly added dropwise again
N-butyl, isobornyl methacrylate, the 1/3~2/3 of hydroxy-ethyl acrylate and mixed solution A, control rate of addition for 1~
Dripped off between 3 hours；Then 1~3 hour is incubated, adds remaining mixed solution A, continue insulation 2~4 hours, discharged.
Described silicon fluoride modified Nano SiO2Preparation process be：First, it is in mass ratio silicon fluoride coupling agent: water:
Isopropanol=1: 10~20: 0.5~1 prepares mixed solution, and mixed solution pH=4.5~6.5 under slightly acidic condition hydrolyze, water
Solution product is fluorine silanol；Then, the Nano-meter SiO_2 for accounting for mixed solution quality 5%~30% is added2, 60~100 under stirring condition
After heating 0.5~2h between DEG C, in 30~50 DEG C of drying, the powder that particle diameter is 1-100nm is ground into, as silicon fluoride is modified and received
Rice SiO2Powder.
Described silicon fluoride modified Nano SiO2Preparation process be：First, it is in mass ratio silicon fluoride coupling agent: water:
Isopropanol=1: 10~20: 0.5~1 prepares mixed solution, and mixed solution pH=4.5~6.5 under slightly acidic condition hydrolyze, water
Solution product is fluorine silanol；Then, the Nano-meter SiO_2 for accounting for mixed solution quality 5%~30% is added2, 60~100 under stirring condition
After heating 0.5~2h between DEG C, in 30~50 DEG C of drying, the powder that particle diameter is 1-100nm is ground into, as silicon fluoride is modified and received
Rice SiO2Powder.
Described silicon fluoride modified Nano SiO2The preparation process of thickened pulp is：Silicon fluoride modified Nano SiO2Powder is with disperseing
After agent in mass ratio 1: 0.2~2 mixes, disperse under 800rpm~2000rpm rotating speeds, after confirmation is completely dissolved, by silicon fluoride
Modified Nano SiO2Powder is 1: 1.5~5 addition organic solvents with organic solvent mass ratio, ball milling 4~8 hours, is discharged, as fluorine
Silane-modified Nano-meter SiO_22Thickened pulp.
The polyurethane/nano SiO of the present invention2Low surface energy anti-fouling paint, it the advantage is that：
(1) by organic silicon monomer be modified obtained acrylic resin have it is higher than traditional acrylic resin hydrophobic
Property, and Nano-meter SiO_22Have by silicon fluoride is modified than unmodified Nano-meter SiO_22High hydrophobicity.
(2) modified Nano-meter SiO_22The nanometer thickened pulp formed after dispersant is handled, can evenly spread to painting
In material, make coating surface that there is homogeneous micro-enzyme electrode, so as to than directly adding Nano-meter SiO_22The coating of formation has more
Beneficial to antifouling surface texture, make aquatic organism be difficult to adhere in coating surface, or even if attachment, also easily rushed by external force such as current
Brush comes off.And this coating does not damage completely without using poisonous anti-fouling agent to environment.
Outer unless specifically stated otherwise in the present invention, involved ratio is mass percent.
Embodiment 1：
Organosilicon modified crylic acid resin accounts for 44%；Polydimethylsiloxaneresins resins account for 10%；Constitution color stuffing accounts for 25%,
Described constitution color stuffing is made up of titanium dioxide, iron oxide red, superfine talcum powder and blanc fixe, and constitution color stuffing is averaged
Granularity is 3 microns, by titanium dioxide: iron oxide red: superfine talcum powder: blanc fixe=1: 4: 6: 20.What silicon fluoride was modified receives
Rice SiO21% is accounted for (by silicon fluoride modified Nano SiO2Contain pure SiO in thickened pulp2Meter)；Organic solvent accounts for 10%, and described is organic
Solvent is dimethylbenzene；Auxiliary agent accounts for 10% (3% levelling agent BYK306,3% anti-settling agent BYK 410 and 4% dispersant B YK110).
In the present embodiment, the preparation method of nano-polyurethane antifouling paint is as follows：
1) using organosilicon modified crylic acid resin as matrix, silicon fluoride modified Nano SiO is added2Thickened pulp, add
Constitution color stuffing, organic solvent, auxiliary agent, 1200rpm is scattered 20 minutes in GFJ-0.4 dispersion machines；
2) polydimethylsiloxaneresins resins are added, it is scattered 20 minutes to continue the 1200rpm in GFJ-0.4 dispersion machines；Then
Ball milling reaches less than 40 μm in 6 hours to fineness in QM-BP ball mills, is discharged after filtering, obtains component one；
3) Isocyanates curing agent 3790 is added in organic solvent dimethylbenzene, Isocyanates curing agent 3790 with
The mass ratio of organic solvent dimethylbenzene is 1: 6, curing agent is dissolved in organic solvent dimethylbenzene, obtains component two；
4) component one being added in component two, the mass ratio of component one and component two is 2: 1, is solidified 5 hours at 20 DEG C,
Low surface energy nano polyurethane anti-fouling paint is formed, for being painted on A3 steel test pieces.
4) component one being added in component two, the mass ratio of component one and component two is 2: 1, is solidified 5 hours at 20 DEG C,
Low surface energy nano polyurethane anti-fouling paint is formed, for being painted on A3 steel test pieces.
In the present embodiment, silicon fluoride (the present embodiment is 17 fluorine decyl trimethoxy silanes) modified Nano SiO2Thickened pulp
Detailed process it is as follows：
Mixed solution is prepared first, and its composition quality ratio is silicon fluoride coupling agent: water: isopropanol=1: 15: 1, mixing is molten
Liquid hydrolyzes in pH=6 hydrochloric acid solution, and hydrolysate is fluorine silanol；Add the Nano-meter SiO_2 for accounting for mixed solution quality 30%2
(in the present embodiment, Nano-meter SiO_22Average grain diameter is 20nm), 2h are heated under stirring condition at 60 DEG C, 40 DEG C of drying, are ground into fluorine
Silane Grafted modified Nano SiO2Powder, wherein silicon fluoride: Nano-meter SiO_22Mass ratio is 0.15: 1, and this powder is silicon fluoride in mass ratio
Modified Nano SiO2Powder: dispersant=1: 1 adds dispersant B YK110, disperses under 1200rpm rotating speeds, confirms to be completely dissolved
Afterwards, silicon fluoride modified Nano SiO in mass ratio2Powder: organic solvent=1: 3 addition organic solvents (dimethylbenzene), ball milling 5 hours,
Obtain silicon fluoride modified Nano SiO2Thickened pulp；
In the present embodiment, by mass percentage, preparing the raw material composition of organosilicon modified crylic acid resin is：Methyl-prop
E pioic acid methyl ester 15%, n-butyl acrylate 10%, isobornyl methacrylate 15%, hydroxy-ethyl acrylate 9.7%；Organosilicon
Monomer 10%, toluene 10%, azodiisobutyronitrile 0.3%, hexone 30%.
Claims (1)
1. a kind of nano-antibacterial antifouling paint, it is characterised in that coating is made up of following two parts：
By mass percentage, component one is formulated by following component and quality proportioning：
By mass percentage, component two is formulated by following component and quality proportioning：
Organic solvent 25~100%；
Curing agent 0~75%；
Count in mass ratio, component one：Component two=2~10:1 mixing, obtains low-surface-energy nano antifouling coating；
The component of the organosilicon modified crylic acid resin is as follows：
The silicon fluoride modified Nano SiO2For Nano-meter SiO_22Surface grafting silicon fluoride, Nano-meter SiO_22Average grain diameter 100nm with
Under, wherein silicon fluoride：Nano-meter SiO_22Mass ratio is 0.05~0.3：1.
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| CN201610475046.8A CN107556856A (en) | 2016-06-27 | 2016-06-27 | A kind of nano-antibacterial antifouling paint |
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| CN201610475046.8A CN107556856A (en) | 2016-06-27 | 2016-06-27 | A kind of nano-antibacterial antifouling paint |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111117400A (en) * | 2019-12-28 | 2020-05-08 | 刘万凯 | Preparation method of dustproof coating |
| CN111826017A (en) * | 2020-07-13 | 2020-10-27 | 同曦集团有限公司 | Antibacterial and antiviral composition, antibacterial and antiviral coating and container |
| CN116462807A (en) * | 2023-03-24 | 2023-07-21 | 箭牌家居集团股份有限公司 | Formula of silica gel, preparation method of silica gel, shower outlet net and shower |
Citations (3)
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| CN102433062A (en) * | 2011-09-15 | 2012-05-02 | 中国科学院金属研究所 | Low surface energy nano polyurethane anti-fouling paint and preparation method thereof |
| CN102807796A (en) * | 2012-06-25 | 2012-12-05 | 浙江省海洋开发研究院 | Novel environment-friendly anti-fouling coating paint for ocean |
| CN104910729A (en) * | 2015-06-23 | 2015-09-16 | 陈良伢 | Environment-friendly nano antimicrobial water-based wood paint |
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2016
- 2016-06-27 CN CN201610475046.8A patent/CN107556856A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102433062A (en) * | 2011-09-15 | 2012-05-02 | 中国科学院金属研究所 | Low surface energy nano polyurethane anti-fouling paint and preparation method thereof |
| CN102807796A (en) * | 2012-06-25 | 2012-12-05 | 浙江省海洋开发研究院 | Novel environment-friendly anti-fouling coating paint for ocean |
| CN104910729A (en) * | 2015-06-23 | 2015-09-16 | 陈良伢 | Environment-friendly nano antimicrobial water-based wood paint |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111117400A (en) * | 2019-12-28 | 2020-05-08 | 刘万凯 | Preparation method of dustproof coating |
| CN111826017A (en) * | 2020-07-13 | 2020-10-27 | 同曦集团有限公司 | Antibacterial and antiviral composition, antibacterial and antiviral coating and container |
| CN116462807A (en) * | 2023-03-24 | 2023-07-21 | 箭牌家居集团股份有限公司 | Formula of silica gel, preparation method of silica gel, shower outlet net and shower |
| CN116462807B (en) * | 2023-03-24 | 2024-01-26 | 箭牌家居集团股份有限公司 | Formula of silica gel, preparation method of silica gel, shower outlet net and shower |
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Application publication date: 20180109 |