CN108441097A - A kind of nanometer of low surface energy anti-fouling paint and preparation method - Google Patents
A kind of nanometer of low surface energy anti-fouling paint and preparation method Download PDFInfo
- Publication number
- CN108441097A CN108441097A CN201810271197.0A CN201810271197A CN108441097A CN 108441097 A CN108441097 A CN 108441097A CN 201810271197 A CN201810271197 A CN 201810271197A CN 108441097 A CN108441097 A CN 108441097A
- Authority
- CN
- China
- Prior art keywords
- parts
- component
- surface energy
- nanometer
- low surface
- 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.)
- Pending
Links
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 69
- 239000003973 paint Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 239000011248 coating agent Substances 0.000 claims abstract description 29
- 238000000576 coating method Methods 0.000 claims abstract description 29
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000002002 slurry Substances 0.000 claims abstract description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 239000010703 silicon Substances 0.000 claims abstract description 17
- 239000004970 Chain extender Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000012948 isocyanate Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 8
- 239000011342 resin composition Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000002270 dispersing agent Substances 0.000 claims description 20
- -1 polysiloxane Polymers 0.000 claims description 19
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 229920001296 polysiloxane Polymers 0.000 claims description 13
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- 239000002518 antifoaming agent Substances 0.000 claims description 10
- 239000006229 carbon black Substances 0.000 claims description 10
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000011324 bead Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- 229920002367 Polyisobutene Polymers 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 239000008236 heating water Substances 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 229920005906 polyester polyol Polymers 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims 1
- 239000006087 Silane Coupling Agent Substances 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- TUVYSBJZBYRDHP-UHFFFAOYSA-N acetic acid;methoxymethane Chemical compound COC.CC(O)=O TUVYSBJZBYRDHP-UHFFFAOYSA-N 0.000 claims 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical group [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 229920002050 silicone resin Polymers 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 230000001681 protective effect Effects 0.000 abstract description 5
- 229920002635 polyurethane Polymers 0.000 description 13
- 239000004814 polyurethane Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 9
- 239000004745 nonwoven fabric Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000010276 construction Methods 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 4
- 239000010445 mica Substances 0.000 description 4
- 229910052618 mica group Inorganic materials 0.000 description 4
- 229910002012 Aerosil® Inorganic materials 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical class O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical compound [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000870659 Crassula perfoliata var. minor Species 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 235000020265 peanut milk Nutrition 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a kind of nanometer of low surface energy anti-fouling paints, which is characterized in that the coating includes organic silicon polyurethane resin Composition and the third component, wherein the organic silicon polyurethane resin Composition is obtained by the reaction by first component and component B；It counts in parts by weight as follows：First component：Isocyanates：20 40 parts；Polyalcohol：10 50 parts；Polyorganosiloxane resin：2 20 parts；Second component：Polyalcohol：40 60 parts；Chain extender：5 20 parts；Catalyst：0.1 5 parts；Third component：38 parts of nano slurry；Curing agent：14 18 parts.The nanometer low surface energy anti-fouling paint and preparation method of the present invention makes coating surface protective materials nanosizing using nano modification technique and polyurethane resin material, reduces surface energy and improves hydrophobicity.
Description
Technical field
The present invention relates to super anticorrosion and antifouling coating material field, more particularly to a kind of nanometer of low surface energy anti-fouling paint with
And preparation method.
Background technology
Hydrophobic low surface energy coat has important application value in fields such as marine anti-pollution, the adherency of low ice, buildings.For
It includes organic siliconresin, fluorine resin, silicon nitrogen resin etc. to prepare the main resin of hydrophobic low surface energy coat.But organosilicon material
Expect that intensity is relatively low, can not be used to the higher occasion of intensity requirement.Fluorine resin generally molding it is more difficult, although by with have
Machine resin carries out cooperation and normal temperature cure may be implemented, but the introducing of organic resin can reduce the intrinsic low-surface-energy of fluorine resin
Feature.The current cost of silicon nitrogen resin is higher, and hardness is high, prepares limited when thick coating.
There are many factor for restricting low surface energy antifouling coating for seas development, including are difficult to obtain the table with more low-surface-energy
Plane materiel material makes its contact angle bigger with water, makes the more difficult adherency of marine growth；Further include that weight easily occurs in the seawater for coating
Structure makes its surface energy increase over time, and is reduced with water contact angle, and marine growth is easy attachment again.
Therefore, existing antifouling paint technology has yet to be improved and developed.
Invention content
The present invention provides a kind of nanometer based on nano modified polyurethane resin low table for the technical problem present on
Face energy antifouling paint and preparation method, make coating surface protective materials nanosizing, reduce surface energy.
In a first aspect, the technical solution that embodiment of the present invention provides is：A kind of nanometer of low surface energy anti-fouling paint is provided,
The coating includes organic silicon polyurethane resin Composition and the third component, wherein the organic silicon polyurethane resin Composition is by first component
It is obtained by the reaction with component B；It counts in parts by weight as follows：First component：Isocyanates：20-40 parts；Polyalcohol：10-50 parts；Poly- silicon
Oxygen alkane resin：2-20 parts；Second component：Polyalcohol：40-60 parts；Chain extender：5-20 parts；Catalyst：0.1-5 parts；Third component：It receives
3-8 parts of Rice ＆ peanut milk；Curing agent：14-18 parts.
Preferably, which is nano-titanium dioxide, polymeric dispersant, propylene glycol methyl ether acetate uniformly mix and
Weight ratio at, nano-titanium dioxide, polymeric dispersant, propylene glycol methyl ether acetate is 1.0: (0.1-0.3): (0.8-
1.0)。
Wherein, which further includes color stuffing, auxiliary agent and solvent, is specifically counted in parts by weight as follows：
Dispersant：0.3-0.5 parts；
Antifoaming agent：0.3-0.5 parts；
Levelling agent：0.1-0.3 parts；
Anti-settling agent：0.5-0.8 parts；
Gas phase of white carbon black：0.4-0.7 parts；
Pigment：15-22 parts；
Filler：3-6 parts.
Polyorganosiloxane resin is linear polysiloxane or the hydroxy-end capped dimethyl silicone polymer of hydrocarbon in the first component, should
Isocyanates is diisocyanate.
The curing agent is amino silicane coupling agent；The polyalcohol includes polyester polyol, polyether polyol, hydroxy-end capped
It is one or more in polyisobutene, hydroxy-end capped polyisoprene, hydroxy-end capped polybutadiene.
The chain extender is the multi-functional alcohols of low molecule quality or aminated compounds that chain extender is hydroxyl or amino.
Second aspect, the technical solution that embodiment of the present invention provides are：A kind of nanometer of low surface energy anti-fouling paint is provided
Preparation method, be as follows：
The preparation of nano slurry：Weight ratio by nano-titanium dioxide, polymeric dispersant, propylene glycol methyl ether acetate is
1.0: (0.1-0.3): after the proportioning mixing of (0.8-1.0), carrying out nanometer bead mill and handle 5-10 times, nano-titanium dioxide is made
Slurry；
The preparation of organic silicon polyurethane resin：First component, component B are obtained by the reaction, and wherein first component is isocyanates, more
First alcohol, polyorganosiloxane resin are formed by prepolymer；Component B is the mixture of polyalcohol, chain extender, glycerine, catalyst；
The preparation of antifouling paint：By the organic silicon polyurethane resin of preparation, prepare nano slurry, color stuffing, auxiliary agent and solvent
Disperse and be ground to fineness to be 30 microns or less by high-speed stirred；The third curing components agent is added, is cured at 20-30 DEG C several
Hour obtained nanometer low surface energy anti-fouling paint.
Wherein, which is prepared as：The polyalcohol is first added in reaction vessel, after heating water removal, is down to room
Temperature adds isocyanates, polyorganosiloxane resin, is to slowly warm up to 90 DEG C, after reacting 2 hours, obtains first component.
The nanometer low surface energy anti-fouling paint and preparation method of the present invention, using nano modification technique and polyurethane resin
Material makes coating surface protective materials nanosizing, reduces surface energy.The polyurethane resin is using the hydroxy-end capped poly dimethyl of hydrocarbon
Siloxanes react forming prepolymer with the structure containing NCO functional groups, by using the polysiloxanes for holding hydrocarbon hydroxyl and gathers
Urethane is combined together, and forms organic silicone polyurethane copolymer, and organosilicon is combined together with polyurethane by C-O-C, a side
Face solves the problems, such as that silicone hydroxyl polysiloxanes is combined with polyurethane to form the water resistance of Si-O-C structures deficiency, on the other hand poly-
Ether or alkyl chain polysiloxanes and polyurethane compatibility are more preferable, and acquired copolymer mechanical strength is obtained better than conventional method
Polysilicone-polyurethanes copolymer so that antifouling paint water resistance is more preferable.
Description of the drawings
Fig. 1 is the use composite construction schematic diagram of the nanometer low surface energy anti-fouling paint of the embodiment of the present invention；And
Fig. 2 is that the another of the nanometer low surface energy anti-fouling paint of the embodiment of the present invention uses composite construction schematic diagram.
Specific implementation mode
Understand in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the accompanying drawings to this hair
Bright embodiment is described in further details.Here, the illustrative embodiments of the present invention and their descriptions are used to explain the present invention, but simultaneously
It is not as a limitation of the invention.
The nanometer low surface energy anti-fouling paint of the present invention, being prepared using nano modification technique and polyurethane resin material is reduced
Surface energy and the good coating of hydrophobic performance.
The coating includes organic silicon polyurethane resin Composition and the third component, wherein the organic silicon polyurethane resin Composition
It is obtained by the reaction by first component and component B.It counts in parts by weight as follows：First component：Isocyanates：20-40 parts；Polyalcohol：10-
50 parts；Polyorganosiloxane resin：2-20 parts；Second component：Polyalcohol：40-60 parts；Chain extender：5-20 parts；Catalyst：0.1-5 parts；
Third component：3-8 parts of nano slurry；Curing agent：14-18 parts.
The nanometer low surface energy anti-fouling paint and preparation method of the present invention, using nano modification technique and polyurethane resin
Material makes coating surface protective materials nanosizing, reduces surface energy and improves hydrophobicity.
Preferably, which is nano-titanium dioxide, polymeric dispersant, propylene glycol methyl ether acetate uniformly mix and
Weight ratio at, nano-titanium dioxide, polymeric dispersant, propylene glycol methyl ether acetate is 1.0: (0.1-0.3): (0.8-
1.0)。
Wherein, which further includes color stuffing, auxiliary agent and solvent, is specifically counted in parts by weight as follows：Dispersant：0.3-
0.5 part；Antifoaming agent：0.3-0.5 parts；Levelling agent：0.1-0.3 parts；Anti-settling agent：0.5-0.8 parts；Gas phase of white carbon black：0.4-0.7
Part；Pigment：15-22 parts；Filler：3-6 parts.
In the present embodiment, the granularity of the nano-titanium dioxide is 20 ± 5 nanometers.
In the present embodiment, auxiliary agent is the common auxiliary agent of paint field, such as：Dispersant, levelling agent, anti-settling agent, antifoaming agent, gas
Phase White Carbon black (aerosil) etc..Wherein：Dispersant can be the Solsperse- of Germany BYK-104s or Britain ICI
4000 dispersants, levelling agent can be the high TEGOFlow300 of German enlightening or U.S. sea name this Bentone27 levelling agent, anti-settling agent
Can be the modest Anti-settlingagent 202P anti-settling agents of Taiwan moral, gas phase of white carbon black can be Degussa Aerosil 200
Gas phase of white carbon black, antifoaming agent can be Germany's 530 antifoaming agent of BYK-A.
In the present embodiment, pigment is titanium dioxide.
In the present embodiment, which is 325 mesh mica powders.Mica powder has good toughness, insulating properties, high temperature resistant, resistance to
The characteristics such as soda acid, corrosion-resistant.Sericite in powder is particularly suitable for making the additive of paint, and the filler of certain uniqueness coating can be big
The big mechanical property for improving coating, the mechanical for enhancing coating is destructive, the features such as preventing from being cracked, change colour, postpone dusting.
In the present embodiment, curing agent is amino silicane coupling agent.
In the present embodiment, polyorganosiloxane resin in the first component be linear polysiloxane or hydrocarbon it is hydroxy-end capped poly- two
Methylsiloxane, the isocyanates are diisocyanate.
In the present embodiment, which includes polyester polyol, polyether polyol, hydroxy-end capped polyisobutene, hydroxyl
It is one or more in the polyisoprene of sealing end, hydroxy-end capped polybutadiene.
In the present embodiment, the chain extender be the multi-functional alcohols of low molecule quality that chain extender is hydroxyl or amino or
Aminated compounds.
The invention further relates to the preparation methods of nanometer low surface energy anti-fouling paint, are as follows：
The preparation of nano slurry：Weight ratio by nano-titanium dioxide, polymeric dispersant, propylene glycol methyl ether acetate is
1.0: (0.1-0.3): after the proportioning mixing of (0.8-1.0), carrying out nanometer bead mill and handle 5-10 times, nano-titanium dioxide is made
Slurry；
The preparation of organic silicon polyurethane resin：First component, component B are obtained by the reaction, and wherein first component is isocyanates, more
First alcohol, polyorganosiloxane resin are formed by prepolymer；Component B is the mixture of polyalcohol, chain extender, glycerine, catalyst；
The preparation of antifouling paint：By the organic silicon polyurethane resin of preparation, prepare nano slurry, color stuffing, auxiliary agent and solvent
Disperse and be ground to fineness to be 30 microns or less by high-speed stirred；The third curing components agent is added, is cured at 20-30 DEG C several
Hour obtained nanometer low surface energy anti-fouling paint.
Wherein, which is prepared as：The polyalcohol is first added in reaction vessel, after heating water removal, is down to room
Temperature adds isocyanates, polyorganosiloxane resin, is to slowly warm up to 90 DEG C, after reacting 2 hours, obtains first component.
Embodiment 1
1, the preparation of nano slurry
By nano-titanium dioxide, Solsperse-4000 polymeric dispersants, propylene glycol methyl ether acetate by weight 1:
After 0.1: 0.8 proportioning mixing, carries out nanometer bead mill and handle 5 times, nano titanium dioxide paste is made.
2, the preparation of nano modified organosilicon polyurethane resin low-surface-energy ship antifouling paint
Nano modified organosilicon polyurethane resin low-surface-energy ship antifouling paint of the present invention is that two groups of first, second is grouped as,
It counts in parts by weight, specific formula is as follows：
First component：
Isocyanates：20-40 parts；
Polyalcohol：10-50 parts；
Polyorganosiloxane resin：2-20 parts；
Second component：
Polyalcohol：40-60 parts；
Chain extender：5-20 parts；
Catalyst：0.1-5 parts；
Third component：
3-8 parts of nano slurry；
Dynasylan AMEO curing agent：16.5 parts.
Wherein, which further includes color stuffing, auxiliary agent and solvent, is specifically counted in parts by weight as follows：BYK-104s points
Powder：0.4 part；
BYK-A530 antifoaming agent：0.4 part；
Bentone27 levelling agents：0.3 part；
Anti-settlingagent 202P anti-settling agents：0.5 part；
200 gas phase of white carbon black of Aerosil：0.4 part；
Titanium dioxide R-960：19.3 parts；
325 mesh mica powders：5 parts；
The preparation of antifouling paint：By the organic silicon polyurethane resin of preparation, prepare nano slurry, color stuffing, auxiliary agent and solvent
After high-speed stirred is uniform, following material is added：Dispersant, antifoaming agent, levelling agent, anti-settling agent, gas phase of white carbon black, face
Then material, filler are fully ground 3 hours in the ball mill with high-speed stirred dispersion machine in 900rpm high speed dispersions 25 minutes, carefully
Degree reaches 30 microns or less；The third curing components agent is added, cures 24 hours obtained nanometer low surface energy anti-fouling paints at 25 DEG C.
The coating has extremely low surface energy and hydrophobic surface preventing material as long-acting ship marine antifouling coating,
Marine growth is set to be hardly adhered to above, play antifouling anti-scaling action.
Embodiment 2
1, the preparation of nano slurry
By nano-titanium dioxide, Solsperse-4000 polymeric dispersants, propylene glycol methyl ether acetate by weight 1:
After 0.15: 0.85 proportioning mixing, carries out nanometer bead mill and handle 6 times, nano titanium dioxide paste is made；
2, the preparation of nano modification poly-organosilicon polyurethane resin low-surface-energy ship antifouling paint
Modified Nano organic silicon polyurethane resin low-surface-energy ship antifouling paint of the present invention is that two groups of first, second is grouped as,
It counts in parts by weight, specific formula is as follows：
First component：
Isocyanates：20-40 parts；
Polyalcohol：10-50 parts；
Polyorganosiloxane resin：2-20 parts；
Second component：
Polyalcohol：40-60 parts；
Chain extender：5-20 parts；
Catalyst：0.1-5 parts；
Third component：
3-8 parts of nano slurry；
Dynasylan AMEO curing agent：16 parts of
Wherein, which further includes color stuffing, auxiliary agent and solvent, is specifically counted in parts by weight as follows：
BYK-104s dispersants：0.5 part；
BYK-A530 antifoaming agent：0.5 part；
Bentone27 levelling agents：0.3 part；
Anti-settlingagent 202P anti-settling agents：0.7 part；
200 gas phase of white carbon black of Aerosil：0.5 part；
Titanium dioxide R-960：20 parts；
325 mesh mica powders：4 parts；
The preparation of antifouling paint：By the organic silicon polyurethane resin of preparation, prepare nano slurry, color stuffing, auxiliary agent and solvent
After high-speed stirred is uniform, following material is added：Dispersant, antifoaming agent, levelling agent, anti-settling agent, gas phase of white carbon black, face
Then material, filler are fully ground 4 hours in the ball mill with high-speed stirred dispersion machine in 1000rpm high speed dispersions 20 minutes,
Fineness reaches 30 microns or less；The third curing components agent is added, cures the obtained antifouling painting of nanometer low-surface-energy in 30 hours at 20 DEG C
Material.
It please refers to Fig.1 and Fig. 2, the invention further relates to a kind of low surface energy anti-fouling paint composite constructions.The low-surface-energy is anti-
Dirty coating composite structure uses the polyurethane low surface energy anti-fouling paint of present disclosure.
The low surface energy anti-fouling paint composite construction includes that the first antifouling paint layer 20, second coated in coating surface 10 is anti-
Dirty dope layer 22 and enhancement layer 30.The enhancement layer 30 is set between the first antifouling paint layer 20 and the second antifouling paint layer 22.
In the present embodiment, which is non-woven fabrics.When being constructed using low surface energy anti-fouling paint, first to the coating surface of matrix 10
Cleaning work is carried out, the iron rust of matrix coating surface 10, dust or other dirt removals is clean, due to low surface energy anti-fouling paint
In humidity or there can be water stain matrix surface to construct, so the water stain of matrix surface need not be removed specially, then clean
Matrix coating surface 10 low surface energy anti-fouling paint is coated as bottom using paint brush or paint spraying apparatus.
In the present embodiment, the thickness of the first antifouling paint layer 20 is 350 microns, waits the low surface energy anti-fouling paint layer attached
Solidification when the coating surface 10, re-lays last layer enhancement layer, such as non-woven fabrics, which plays further reinforcement
Effect is spaced 8~24 hours after being laid with non-woven fabrics, and the time determines according to construction environment, then coats one again on non-woven fabrics
Layered low-surface energy antifouling paint layer is as the second antifouling paint layer 22, and the thickness of the second antifouling paint layer 22 is 420 microns, figure
1 illustrated embodiment is using three-decker and overall thickness is up to 800 microns or more.
As shown in Fig. 2, in another embodiment, two layers of enhancement layer can be arranged.The thickness of the first antifouling paint layer 40
It is 350 microns, waits the low surface energy anti-fouling paint layer attachment solidification when coating surface 10, re-lay the first enhancement layer of last layer
52, such as non-woven fabrics.It is spaced 8~24 hours after being laid with non-woven fabrics, then applies the low table of last layer again on first enhancement layer 52
For face energy antifouling paint layer as the second antifouling paint layer 42, the thickness of the second antifouling paint layer 42 is 420 microns, waits the low table
Face energy antifouling paint layer attachment solidification re-lays the second enhancement layer of last layer 54, such as non-woven fabrics when the coating surface 10.It is laid with
It is spaced after non-woven fabrics 8~24 hours, then coats a layered low-surface energy antifouling paint layer conduct again on second enhancement layer 54
The thickness of third antifouling paint layer 44, the third antifouling paint layer 44 is 420 microns.Wherein, first enhancement layer 52 and second
Enhancement layer 54 also functions to further booster action.
The low surface energy anti-fouling paint composite construction of the present embodiment can be effectively protected the coating surface 10 of matrix not by outer
The influence of boundary's environment or rugged environment and corroded.It is required according to the construction requirement of coating surface 10 and protection, the low surface
The thickness of energy antifouling paint layer is changeable.
The nanometer low surface energy anti-fouling paint and preparation method of the present embodiment, using nano modification technique and polyurethane tree
Fat material makes coating surface protective materials nanosizing, reduces surface energy.The polyurethane resin is using the hydroxy-end capped poly- diformazan of hydrocarbon
Radical siloxane react forming prepolymer with the structure containing NCO functional groups, by using end hydrocarbon hydroxyl polysiloxanes with
Polyurethane is combined together, and forms organic silicone polyurethane copolymer, and organosilicon is combined together with polyurethane by C-O-C, and one
Aspect solves the problems, such as that silicone hydroxyl polysiloxanes is combined with polyurethane to form the water resistance of Si-O-C structures deficiency, another aspect
Polyethers or alkyl chain polysiloxanes and polyurethane compatibility are more preferable, and acquired copolymer mechanical strength is obtained better than conventional method
Obtain polysilicone-polyurethanes copolymer so that antifouling paint water resistance is more preferable.
Mode the above is only the implementation of the present invention is not intended to limit the scope of the invention, every to utilize this
Equivalent structure or equivalent flow shift made by description of the invention and accompanying drawing content, it is relevant to be applied directly or indirectly in other
Technical field is included within the scope of the present invention.
Claims (8)
1. a kind of nanometer of low surface energy anti-fouling paint, which is characterized in that the coating include organic silicon polyurethane resin Composition with
And third component, wherein the organic silicon polyurethane resin Composition is obtained by the reaction by first component and component B；It counts in parts by weight such as
Under：
First component：
Isocyanates：20-40 parts；
Polyalcohol：10-50 parts；
Polyorganosiloxane resin：2-20 parts；
Second component：
Polyalcohol：40-60 parts；
Chain extender：5-20 parts；
Catalyst：0.1-5 parts；
Third component：
3-8 parts of nano slurry；
Curing agent：14-18 parts.
2. according to claim 1 nanometer of low surface energy anti-fouling paint, which is characterized in that the nano slurry is nano-silica
Change titanium, polymeric dispersant, propylene glycol methyl ether acetate are uniformly mixed, nano-titanium dioxide, polymeric dispersant, the third two
The weight ratio of alcohol methyl ether acetate is 1.0: (0.1-0.3): (0.8-1.0).
3. according to claim 2 nanometer of low surface energy anti-fouling paint, which is characterized in that third component further includes that face is filled out
Material, auxiliary agent and solvent are specifically counted as follows in parts by weight：
Dispersant：0.3-0.5 parts；
Antifoaming agent：0.3-0.5 parts；
Levelling agent：0.1-0.3 parts；
Anti-settling agent：0.5-0.8 parts；
Gas phase of white carbon black：0.4-0.7 parts；
Pigment：15-22 parts；
Filler：3-6 parts.
4. according to the nanometer low surface energy anti-fouling paint described in claim 1-3 any one, which is characterized in that the first component
Middle polyorganosiloxane resin is linear polysiloxane or the hydroxy-end capped dimethyl silicone polymer of hydrocarbon, and the isocyanates is two different
Cyanate.
5. according to claim 4 nanometer of low surface energy anti-fouling paint, which is characterized in that the curing agent is amino silane
Coupling agent；The polyalcohol includes polyester polyol, polyether polyol, hydroxy-end capped polyisobutene, hydroxy-end capped poly- different
It is one or more in pentadiene, hydroxy-end capped polybutadiene.
6. according to claim 5 nanometer of low surface energy anti-fouling paint, which is characterized in that the chain extender is that chain extender is
The multi-functional alcohols of low molecule quality or aminated compounds of hydroxyl or amino.
7. the preparation method of a kind of nanometer of low surface energy anti-fouling paint, which is characterized in that be as follows：
The preparation of nano slurry：It is 1.0 by the weight ratio of nano-titanium dioxide, polymeric dispersant, propylene glycol methyl ether acetate:
(0.1-0.3): it after the proportioning mixing of (0.8-1.0), carries out nanometer bead mill and handles 5-10 times, nano titanium dioxide paste is made；
The preparation of organic silicon polyurethane resin：First component, component B are obtained by the reaction, wherein first component be isocyanates, polyalcohol,
Polyorganosiloxane resin is formed by prepolymer；Component B is the mixture of polyalcohol, chain extender, glycerine, catalyst；
The preparation of antifouling paint：By the organic silicon polyurethane resin of preparation, prepare nano slurry, color stuffing, auxiliary agent and solvent process
High-speed stirred disperses and is ground to fineness to be 30 microns or less；The third curing components agent is added, cures several hours at 20-30 DEG C
Nanometer low surface energy anti-fouling paint is made.
8. the preparation method of according to claim 7 nanometer of low surface energy anti-fouling paint, which is characterized in that the first component
Be prepared as：The polyalcohol is first added in reaction vessel, after heating water removal, is down to room temperature, adds isocyanates, gather
Silicone resin is to slowly warm up to 90 DEG C, after reacting 2 hours, obtains first component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810271197.0A CN108441097A (en) | 2018-03-29 | 2018-03-29 | A kind of nanometer of low surface energy anti-fouling paint and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810271197.0A CN108441097A (en) | 2018-03-29 | 2018-03-29 | A kind of nanometer of low surface energy anti-fouling paint and preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108441097A true CN108441097A (en) | 2018-08-24 |
Family
ID=63197732
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810271197.0A Pending CN108441097A (en) | 2018-03-29 | 2018-03-29 | A kind of nanometer of low surface energy anti-fouling paint and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108441097A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109536013A (en) * | 2018-12-28 | 2019-03-29 | 中国船舶重工集团公司第十二研究所 | A kind of preparation method of the hydrophobic nonpolluting coating of graphene in-situ preparation of graft modification |
| CN110003702A (en) * | 2019-04-22 | 2019-07-12 | 成都新柯力化工科技有限公司 | A kind of low-surface-energy is water-fast antifouling building coating additive and preparation method |
| CN112210289A (en) * | 2020-09-24 | 2021-01-12 | 常熟理工学院 | Polyurethane marine antifouling paint with super-hydrophobic and self-healing performances |
| CN112625595A (en) * | 2020-12-08 | 2021-04-09 | 中国科学院海洋研究所 | Nano synergistic low surface energy antifouling composition and preparation method thereof |
| CN115746691A (en) * | 2022-10-14 | 2023-03-07 | 中国船舶重工集团公司第七一九研究所 | Water-blocking material for sealing open pores of heat-insulating material and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618165A (en) * | 2012-03-20 | 2012-08-01 | 中国科学院金属研究所 | Nanometer polysiloxane nontoxic low-surface-energy ship antifouling coating and preparation method thereof |
| WO2012146023A1 (en) * | 2011-04-25 | 2012-11-01 | Dow Global Technologies Llc | Moisture curable compositions and low surface energy coating compositions made therefrom |
| CN103483526A (en) * | 2013-08-20 | 2014-01-01 | 中科院广州化学有限公司 | Organic silicon graft modification polyester type polyurethane prepolymer and preparation and application thereof |
| CN103694839A (en) * | 2013-12-16 | 2014-04-02 | 浙江大学 | Preparation method of antibacterial low-surface energy modified polyurethane antifouling coating agent |
| CN104558494A (en) * | 2015-01-22 | 2015-04-29 | 泉州市德诚高新树脂有限公司 | Highly moisture permeable modified polyurethane and preparation method thereof |
-
2018
- 2018-03-29 CN CN201810271197.0A patent/CN108441097A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012146023A1 (en) * | 2011-04-25 | 2012-11-01 | Dow Global Technologies Llc | Moisture curable compositions and low surface energy coating compositions made therefrom |
| CN102618165A (en) * | 2012-03-20 | 2012-08-01 | 中国科学院金属研究所 | Nanometer polysiloxane nontoxic low-surface-energy ship antifouling coating and preparation method thereof |
| CN103483526A (en) * | 2013-08-20 | 2014-01-01 | 中科院广州化学有限公司 | Organic silicon graft modification polyester type polyurethane prepolymer and preparation and application thereof |
| CN103694839A (en) * | 2013-12-16 | 2014-04-02 | 浙江大学 | Preparation method of antibacterial low-surface energy modified polyurethane antifouling coating agent |
| CN104558494A (en) * | 2015-01-22 | 2015-04-29 | 泉州市德诚高新树脂有限公司 | Highly moisture permeable modified polyurethane and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 巴淼等: "有机硅防污涂料的研究进展", 《表面技术》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109536013A (en) * | 2018-12-28 | 2019-03-29 | 中国船舶重工集团公司第十二研究所 | A kind of preparation method of the hydrophobic nonpolluting coating of graphene in-situ preparation of graft modification |
| CN110003702A (en) * | 2019-04-22 | 2019-07-12 | 成都新柯力化工科技有限公司 | A kind of low-surface-energy is water-fast antifouling building coating additive and preparation method |
| CN112210289A (en) * | 2020-09-24 | 2021-01-12 | 常熟理工学院 | Polyurethane marine antifouling paint with super-hydrophobic and self-healing performances |
| CN112625595A (en) * | 2020-12-08 | 2021-04-09 | 中国科学院海洋研究所 | Nano synergistic low surface energy antifouling composition and preparation method thereof |
| CN115746691A (en) * | 2022-10-14 | 2023-03-07 | 中国船舶重工集团公司第七一九研究所 | Water-blocking material for sealing open pores of heat-insulating material and application thereof |
| CN115746691B (en) * | 2022-10-14 | 2023-11-17 | 中国船舶重工集团公司第七一九研究所 | Water-blocking material for closing open pores of heat insulating material and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108441097A (en) | A kind of nanometer of low surface energy anti-fouling paint and preparation method | |
| DE602004008793T2 (en) | HAFTSCHICHTMASSE WITH AT LEAST TWO PIECES OF FUNCTIONAL POLYSILOXAN COMPOUNDS AND CORRESPONDING USE | |
| CN104403548B (en) | Containing polyether polyol/nano-TiO2the aqueous polyurethane coating of hybrid material | |
| JP6270979B2 (en) | Curable organopolysiloxane antifouling composite coating and antifouling substrate coated with the composite coating | |
| EP2921538B1 (en) | Antifouling coating composition, antifouling coating film, antifouling substrate, and method for improving storage stability of antifouling coating composition | |
| EP2617778B1 (en) | Fouling release coatings | |
| JP4195537B2 (en) | Curable composition, coating composition, paint, antifouling paint, cured product thereof, and substrate antifouling method | |
| JP7208900B2 (en) | Water-based coating agent composition, and water-based lubricating coating composition comprising the same | |
| CN102482514A (en) | Adhesion promoter for coatings on different substrate surfaces | |
| JP2015157959A (en) | Aggregates having attached polymer groups and polymer foams | |
| CN110484128A (en) | A kind of hydrogel-organosilicon bionic gradient antifouling paint and preparation method thereof | |
| CN107428614B (en) | Curable grouting composition comprising alkoxysilyl-terminated urethane group-containing polymer, silicone resin, surfactant and aggregate | |
| CN106833333B (en) | A kind of aqueous anti-doodling paint and preparation method thereof | |
| CN102618165A (en) | Nanometer polysiloxane nontoxic low-surface-energy ship antifouling coating and preparation method thereof | |
| CN104893569A (en) | Silica sol enhanced organic silicon antifouling paint and preparation method thereof | |
| CN104119751B (en) | A kind of nano enamel and preparation method thereof for aircraft skin | |
| CN108570273A (en) | A kind of solvent-free graphene oxide-glass flake anticorrosion paint and preparation method thereof | |
| WO2018123928A1 (en) | Anti-fouling paint composition, anti-fouling paint film, base material having anti-fouling paint film attached thereto and method for producing same, and fouling prevention method | |
| CN110903726A (en) | Environment-friendly decoration paint and preparation method thereof | |
| CN106243314A (en) | A kind of composite modified aqueous polyurethane and preparation method and application | |
| CN208667572U (en) | A kind of nanometer of low surface energy anti-fouling paint composite construction | |
| CN110066583B (en) | Modified alkyd resin coating and preparation method thereof | |
| CN107216799A (en) | A kind of court environment-friendly water-based polyurethane paint vehicle and aqueous polyurethane finish paint | |
| CN109233606A (en) | A kind of multiple cross-linked polyurethane coating composition of high abrasion organosilicon and preparation method thereof | |
| CN110093086A (en) | The processing technology of waterborne epoxy floor paint |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180824 |