CN101591494B - Antifogging coating, special antifogging coating composition and antifogging product thereof - Google Patents
Antifogging coating, special antifogging coating composition and antifogging product thereof Download PDFInfo
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- CN101591494B CN101591494B CN2009100883189A CN200910088318A CN101591494B CN 101591494 B CN101591494 B CN 101591494B CN 2009100883189 A CN2009100883189 A CN 2009100883189A CN 200910088318 A CN200910088318 A CN 200910088318A CN 101591494 B CN101591494 B CN 101591494B
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Abstract
The invention discloses an antifogging coating, a special antifogging coating composition and a special antifogging product thereof. The antifogging coating composition comprises the following components: 0.5 to 58 mass portions of homopolymer or copolymer taking acrylic acid or methylacrylic acid as a monomer, 0.05 to 6 mass portions of aziridine crosslinking agent, 0.5 to 58 mass portions of inorganic nano-particles and 40 to 98 mass portions of solvent. The coating composition has excellent antifogging property and excellent water resistance; the coating has high bonding strength with a substrate; and the antifogging coating formed by coating the substrate of the coating has good surface hardness. The antifogging product coated with the antifogging coating has excellent surface smoothness and clearness, excellent appearance, high surface strength and good wear resistance, and can be used for bathroom mirrors, eyeglasses, helmets, safety glasses, automobile lampshades, instrument panels and the like.
Description
Technical field
The present invention relates to a kind of antifogging coating and special-purpose anti fogging coating composite and antifog article.
Background technology
Object or material that a large amount of and optical correlation are arranged in the life, for example, vehicle glass, the window glass of buildings, bathroom mirror, instrument instrument dish, glasses, safety glasses or the like.Yet, in high humidity or there is the place of the big temperature difference, will form the mist that influences sight line easily on these or printing opacity or the reflective optical surface.Mist has brought a lot of inconvenience to daily life, sometimes or even catastrophic.For example at the vehicle window of automobile that travelling, usually in rainy season or colder winter, surface knot mist is inevitable.General way is to utilize air-conditioning blowing heatable vehicle window surface now, improves the condensation point of water, thereby makes the vehicle window surface be in dry status, prevents to tie mist with this and guarantees visibility meter.
The formation of mist is to have formed the globule of diameter 100nm to 400nm because steam condenses in body surface under the driving of the temperature difference.These globules because of its size can with wavelength of visible light generation diffraction and interference, have influence on the propagation of light, thereby it is fuzzy to cause clearly visual surface to take place.Surface knot mist has brought a lot of inconvenience for undoubtedly production and life, and therefore antifog in recent years technology progressively is subject to people's attention.Antifog method mainly is divided into electric heating process at present and uses the anti-fog function coating.The former is effective, but the cost height, and need be cost to consume the extra energy, this theme with current energy-conserving and environment-protective is contrary to.Therefore, present more work concentrates on the development research to the function anti-fog coating.And can be divided into two kinds of hydrophobic type and hydrophilics for the anti-fog function coating.Yet the antifogging coating of hydrophobic type also stays in the stage of notion up to now, be difficult to realize among the reality, even if can realize also because cost is too high, technology is too complicated and can't be applied in the actual production life.The anti-fog coating research of hydrophilic is many.Can be divided into two kinds in principle: 1, surfactant method; 2, hydrophilic molecules coating.Surfactant method: can be tensio-active agent directly apply or by with the tensio-active agent blend in other one-tenth membrane matrix.Becoming membrane matrix can be that organic materials also can be an inorganic materials, and its principle of work all is " stripping " that comes from surfactant molecule.Because the stripping of surfactant molecule is in being condensate in its surperficial water, thereby reduced the surface tension (having reduced the contact angle of water) of this water, made the globule be easier to form moisture film but not the globule at surface spreading on the surface.Because of forming nano level droplet, just can not have influence on the optical property on surface.This method no doubt effect is fine, comes from the mode of its this " sacrifice " formula---and constantly with the surfactant molecule stripping, it must be unabiding being doomed the effect of this antifogging coating, promptly volatile antifog.If tensio-active agent is by reducing adversary---the surface energy of water, hydrophilic molecules coating rule is to sprawl by what the surface energy that improves self was realized surface condensation water that (water is little at the high surface energy surface contact angle so, and the low surface energy surface contact angle is big), effect is the same also to be to allow the globule be transformed into moisture film, but a kind of really nonvolatil anti-fog function coating that this method obtains.So being considered to a kind of practical methods the most, the method for hydrophilic molecules coating has been subjected to paying close attention to the most widely and research.
Hydrophilic molecules can be divided into the inorganic hydrophilic molecule usually, hydrophilic molecules three classes of organic hydrophilic polymer and hybrid.The inorganic hydrophilic molecule can be silicon-dioxide or titanium dioxide.The wetting ability of silicon-dioxide makes that because of its surface polarity group silicon hydroxyl limited amount its anti-fog effect is very general.Can recognize that by more existing patents it often needs the matching surface promoting agent to use and just can obtain anti-preferably fog effect, for example: WO1996018691, US 20050163924, JP2007126672 A, US005997621A, JP2007126672, US005873931A2 and US005753373A, but along with flowing away of surfactant molecule, its antifog property also reduces gradually.In addition; titanium dioxide surface can produce very active free radical under ultraviolet irradiation; (US6013372) thus these free radicals can be bonded to the water molecules on surface the surface energy that the surface is improved on its surface; in case can ultraviolet stop irradiation, original state than low surface energy will drive in the wrong direction back on this surface.So this have higher dependent material and also often be difficult in actual applications promote.At present, at the maximum still hydrophilic high molecular polymer of anti-fog function coatings art research.These polymkeric substance all have some polar groups, for example hydroxyl, carboxyl, amino, amide group, sulfonic group or the like usually.Macromolecule filming matrix can be divided into acrylate or urethane series.This class patent has WO 1993023471 A1, US 3700487, US4567221 A, US 3484157, US 6531215 B, EP 770658 B1, JP10212471 A, CN 1265408A, CN1662466A, CN 1472268A, CN 1070219C, CN 101238187A, CN 1098429A, CN1724608A and CN 1158881A or the like.The hydrophilic molecules antifogging coating of an other class hybrid has very many patents too.For example: US4478909 A, EP52427 A1 and US3773776 or the like.
These antifogging coatings of having reported all have certain anti-fog effect, but all there is weak point in every kind of method, or anti-fog duration is not enough, or antifogging surface hardness is too poor, or water tolerance is bad, or production cost is too high.The surface of the high surface energy that forms with hydrophilic macromolecule, its wetting ability and hardness is two aspects of contradiction often, are difficult to it perfectly is unified in the same system.Why so much about antifog patent and reported in literature so far this also be, and from the produce market angle, sophisticated anti-fog function coating is not seen the reason of promoting widely so far yet.
Summary of the invention
The purpose of this invention is to provide a kind of antifogging coating and special-purpose anti fogging coating composite thereof.
Anti fogging coating composite provided by the present invention, its composition comprises following component: the sour with acrylic or methacrylic of 0.5-58 mass parts is monomeric homopolymer or multipolymer, 0.05-6 the aziridine crosslinker of mass parts, the solvent of the inorganic nano-particle of 0.5-58 mass parts and 40-98 mass parts.
Wherein, the molecular-weight average of described homopolymer or multipolymer can be 500-50000Da, preferred 1000-10000Da.
Described multipolymer is specifically formed by Acrylic Acid Monomer or methacrylic acid monomer and following at least a monomer polymerization: vinylformic acid (2-hydroxyethyl) ester, 2-hydroxypropyl acrylate, methacrylic acid (2-hydroxyethyl) ester, methacrylic acid (2-hydroxypropyl) ester, vinylformic acid (3-hydroxypropyl) ester, methacrylic acid (3-hydroxypropyl) ester, acrylamide-2-methyl-propyl sulfonic acid, Methacrylamide-2-methyl-propyl sulfonic acid, acrylamide, Methacrylamide, glycidyl acrylate, glycidyl methacrylate, propenyl alkane ether hydroxyl sodium sulfonate, compound shown in vinyl alcohol and the formula I;
(formula I)
Among the formula I,
R
1Be H or CH
3
R
2Be C
N 'H
2n '+1N ' is the integer of 0-12, or (CH
2CH
2O)
N "N " is the integer of 1-20;
R
3Be OH, NH
2, SO3H or C
N 'H
2n '+1, n ' is the integer of 0-12;
X is O, NH or NR
2R
3
N is the integer of 1-100, and m is the integer of 1-100;
Described aziridine crosslinker is the water-based multi-group crosslink agent, and the functional group's number in the described aziridine crosslinker is more than or equal to 2.The commercial product of preferred use is as CX100, Sa100 etc.
Described inorganic nano-particle specifically can be oxide nano-particles; The particle size range of described oxide nano-particles is 2-200nm, is preferably 2-100nm, more preferably 2-50nm.
Described oxide nano-particles specifically can be Nano particles of silicon dioxide, titanium dioxide nano-particle or both mixtures.
Described solvent can be water, alcohol or both mixtures; Described alcohol can be these alcohol commonly used such as methyl alcohol, ethanol, Virahol.
The component of described anti fogging coating composite also can comprise the catalyzer of 0.01-0.1 mass parts.Described catalyzer can be mineral acid or organic acid, example hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, Glacial acetic acid or other heteropolyacid.
The component of anti fogging coating composite of the present invention except said components, also can comprise additive commonly used in the coating, as flow agent, coupling agent, oxidation inhibitor and film coalescence aid.Coupling agent commonly used has silane coupling agent, and the adding of coupling agent can promote the interaction between organic phase polymer and the inorganic nano-particle phase, thereby increases the intensity by the formed coating of coating.
Antifogging coating provided by the present invention is prepared by following method: anti fogging coating composite provided by the present invention is coated on the matrix, forms described antifogging coating after solidifying.
Wherein, described matrix can be resin, and described resin can be thermoplastic resin or thermosetting resin, comprises polyethylene terephthalate (PET), polycarbonate (PC), polymethylmethacrylate (PMMA), polypropylene (PP) or other transparent macromolecule resin.
The method of described coating can adopt the method for dip-coating, spraying, roller coating or brushing according to the situation of resinous substrates; Described solidified method is at 50-150 ℃ of dry 2-30min.
A further object of the present invention provides a kind of antifog article.
Antifog article provided by the present invention is the transparent resin product that is coated with antifogging coating of the present invention; The thickness of described antifogging coating is 0.2-100 μ m, specifically can be 0.5-80 μ m, 0.5-50 μ m, 0.5-30 μ m, 0.5-10 μ m etc.
Coating composition provided by the present invention has excellent antifog property, excellent water tolerance, the cohesive strength height of this coating and matrix, and the antifogging coating that forms with this coating coating substrate has surface of good hardness.The antifog article that is coated with described antifogging coating has surface of good slipperiness and clarity, and good appearance, surface strength height, wear resistance are good, can will be used for bathroom mirror, glasses, the helmet, safety precaution glasses, automobile lamp cover and instrument instrument dish or the like.
Embodiment
Following embodiment only is used to illustrate in greater detail the present invention, rather than is used to limit the scope of the invention.
Employed per-cent among the following embodiment all is meant mass percent; Described experimental technique if no special instructions, is ordinary method; Described reagent and material if no special instructions, all can obtain from commercial channels.
The physical properties of the antifog article that embodiment makes is estimated with following method.
1) antifog property
Sample is positioned on 50 ℃ of saturated vapors, and by observing, if do not haze in 1 minute, it is antifog qualified then to be considered as.
2) wear resistance
A) measure hardness according to the relevant entry of JIS K 5651-1966 method mensuration pencil hardness.
B) according to ASTM D3363-92a or ECCA T4 method, with instrument JM-IV type abrasion instrument, reciprocating friction is 500 times under the condition of loading 750g, represents its Taber abradability with the velocity of variation of surveying coating.
3) cementability
Film with cross cut, form 10 * 10 grid.(cello tape) adheres to outermost surface with the 3M-610 Pressuresensitive Tape, tears adhesive tape off along 90 degree directions then.The grid number of the coating that calculating is torn off, and if less than 5% would be regarded as qualified.
4) water tolerance
Sample was soaked in 50 ℃ the distilled water 300 hours, if its antifog property remains unchanged, it is qualified then to be considered as.
5) ultra-violet resistance
QUV test 500 hours, test reference standard ASTM G-155, first ultra violet lamp that is circulated in 62 ℃ of xenon arc light source was sprayed water 18 minutes after 120 minutes.Total test duration is 500 hours.The ultra-violet resistance that shows antifogging coating can not pass through if the antifog property behind the uv irradiating does not descend.
Embodiment 1, preparation have the PET goods of antifogging coating
The aqueous solution with 100g 60% poly acrylic acid-poly acrylamide-2-methyl propane sulfonic acid (the calm and peaceful water treatment in Shandong company limited) (molecular-weight average is 2000Da), 1.5g aziridine crosslinker CX100 (DSM company), the 10g particle diameter is Nano particles of silicon dioxide (the Nissan ChemicalIndustries of Japanese Nissan company of 20nm, Ltd.) the water-sol (concentration is 50%) mixes, adding a small amount of concentration in said mixture is the hydrochloric acid of 1mol/L, regulating the pH value is 2 to 4, adds 0.3g silane coupling agent TEOS (tetraethoxy) (Beijing lean chemical industry) in addition again.With the line rod said mixture is coated PET (polyethylene terephthalate) surface, in 120 ℃ of dryings 5 minutes, obtaining antifogging coating thickness was the PET goods of 1 μ m with PET.
Measuring physical properties:
Antifog property:＞1 minute (50 ℃ of water vapors), qualified;
Surface hardness: 2H;
Wear resistance (750g, 500r) g:0.01;
Cohesiveness:＞95%, qualified;
Water tolerance:＞300 hours, qualified;
Ultra-violet resistance:＞500 hours, qualified.
Embodiment 2, preparation have the PC goods of antifogging coating
The aqueous solution with 100g 40% poly acrylic acid-poly acrylamide-2-methyl propane sulfonic acid-polyacrylic acid (2-hydroxyethyl) ester (the calm and peaceful water treatment in Shandong company limited) (molecular-weight average is 2000 Da), 4g aziridine crosslinker CX100, the 200g particle diameter is that the Nano particles of silicon dioxide water-sol (concentration is 30%) of 8nm mixes, adding a small amount of concentration in said mixture is the hydrochloric acid of 1mol/L, regulating the pH value is 2 to 4, adding 3g silane coupling agent KH560 (glycidyl ether propyl trimethoxy silicane) (energy Dehua, Nanjing worker company limited) in addition again stirs, with the line rod said mixture is coated PC (polycarbonate) surface, in 150 ℃ of dryings 2 minutes, obtaining antifogging coating thickness was the PC goods of 5 μ m with PC.
Measuring physical properties:
Antifog property:＞1 minute (50 ℃ of water vapors), qualified;
Surface hardness: H;
Wear resistance (750g, 500r) g:0.03;
Cohesiveness:＞95%, defective;
Water tolerance:＞300 hours, qualified.
Ultra-violet resistance:＞500 hours, qualified.
Embodiment 3, preparation have the PMMA goods of antifogging coating
The aqueous solution with 100g 30% polyacrylic acid-propenyl alkane ether hydroxyl sodium sulfonate (Aldrich import reagent) (molecular-weight average is 7000 Da), 0.3g aziridine crosslinker CX100, the 100g particle diameter is that the Nano particles of silicon dioxide water-sol (concentration is 30%) of 5nm mixes, adding a small amount of concentration in said mixture is the hydrochloric acid of 1mol/L, regulating the pH value is 2 to 4, adding 2.5g silane coupling agent TEOS (tetraethoxy) in addition again stirs, with the line rod said mixture is coated the PMMA surface, in 100 ℃ of dryings 15 minutes, obtaining antifogging coating thickness was the PMMA goods of 2 μ m with PMMA.
Measuring physical properties:
Antifog property:＞1 minute (50 ℃ of water vapors), qualified;
Surface hardness: H;
Wear resistance (750g, 500r) g:0.03;
Cohesiveness:＜95%, defective;
Water tolerance:＞300 hours, qualified.
Ultra-violet resistance:＞500 hours, qualified.
Embodiment 4, preparation have the PET goods of antifogging coating
Preparation poly acrylic acid-poly acrylamide-2-methyl propane sulfonic acid-polyacrylic acid glycidyl ester:
With 10g vinylformic acid; 4g acrylamide-2-methyl propane sulfonic acid; the 2g glycidyl acrylate is dissolved in the 25g water; be heated to 65 ℃; nitrogen protection adds 100 milligrams of Ammonium Persulfate 98.5s down then; reactive polymeric 6 hours, obtaining molecular-weight average is poly acrylic acid-poly acrylamide-2-methyl propane sulfonic acid-polyacrylic acid glycidyl ester of 2000Da.
The aqueous solution with 100g 37% poly acrylic acid-poly acrylamide-2-methyl propane sulfonic acid-polyacrylic acid glycidyl ester (molecular-weight average is 2000Da), 2g aziridine crosslinker CX100, the 10g particle diameter is that the Nano particles of silicon dioxide water-sol (concentration is 50%) of 60nm mixes, adding a small amount of concentration in said mixture is the hydrochloric acid of 1mol/L, regulating the pH value is 2 to 4, adding 0.15g silane coupling agent TEOS (tetraethoxy) in addition again stirs, with the line rod said mixture is coated the pet sheet face, in 120 ℃ of dryings 5 minutes, obtaining antifogging coating thickness was the PET goods of 0.5 μ m with PET.
Measuring physical properties:
Antifog property:＞1 minute (50 ℃ of water vapors), qualified;
Surface hardness: 2H;
Wear resistance (750g, 500r) g:0.01;
Cohesiveness:＞95%, defective;
Water tolerance:＞300 hours, qualified
Ultra-violet resistance:＞500 hours, qualified.
Embodiment 5, preparation have the PET goods of antifogging coating
Preparation polyacrylic acid-glycidyl acrylate: with 10g vinylformic acid; the 4g glycidyl acrylate is dissolved in the 25g water; be heated to 65oC; nitrogen protection adds 50 milligrams of Ammonium Persulfate 98.5s down then; reactive polymeric 6 hours obtains molecular-weight average and is polyacrylic acid-glycidyl acrylate of 4000.
The aqueous solution with 100g 40% polyacrylic acid-glycidyl acrylate (molecular-weight average is 4000 Da), 3g polyfunctional group aziridine crosslinker CX100, the 15g particle diameter is that the Nano particles of silicon dioxide water-sol (concentration is 30%) of 90nm mixes, adding a small amount of concentration in said mixture is the hydrochloric acid of 1mol/L, regulating the pH value is 2 to 4, stir at adding 0.1g silane coupling agent TEOS (tetraethoxy) in addition, with the line rod said mixture is coated the pet sheet face, in 120 ℃ of dryings 5 minutes, obtaining antifogging coating thickness was the PET goods of 5 μ m with PET.
Measuring physical properties:
Antifog property:＞1 minute (50 ℃ of water vapors), qualified;
Surface hardness: 2H;
Wear resistance (750g, 500r) g:0.01;
Cohesiveness:＞95%, qualified;
Water tolerance:＞300 hours, qualified;
Ultra-violet resistance:＞500 hours, qualified.
Embodiment 6, preparation have the PET goods of antifogging coating
Preparation poly acrylic acid-poly vinyl alcohol (reference " chemical research and the application " fourth phase in 2009), concrete preparation method is as follows: the VAc vinyl acetate is added in the there-necked flask, charge into nitrogen and get rid of the interior oxygen of reactor, heating in water bath, temperature control is in 65 ℃, added the methanol solution of vinylformic acid and Diisopropyl azodicarboxylate in 10 minutes later on, react after 5 hours, the methanol solution that adds excess NaOH, in and behind the carboxyl, unnecessary NaOH catalyzed alcoholysis reaction, obtain vinylformic acid-polyvinyl alcohol P (VA-co-AA), final product was put into 75 ℃ of oven dryings 2 hours, in 100 ℃ of vacuum drying ovens dry 1 hour again, solid is weighed.
The aqueous solution with 100g 20% poly acrylic acid-poly vinyl alcohol (molecular-weight average is 5000), 1.5g polyfunctional group aziridine crosslinker CX100, the 30g particle diameter is that the Nano particles of silicon dioxide water-sol (concentration is 30%) of 45nm mixes, in said mixture, add the hydrochloric acid that a small amount of concentration is 1mol/L again, regulating the pH value is 2 to 4, stir at adding 0.2g silane coupling agent KH560 (Racemic glycidol propyl trimethoxy silicane) in addition, with the line rod said mixture is coated the pet sheet face, in 80 ℃ of dryings 30 minutes, obtaining antifogging coating thickness was the PET goods of 2 μ m with PET.
Measuring physical properties:
Antifog property:＞1 minute (50 ℃ of water vapors), qualified;
Surface hardness: HB;
Wear resistance (750g, 500r) g:0.05;
Cohesiveness:＜95%, defective;
Water tolerance:＜300 hours, defective;
Ultra-violet resistance:＜500 hours, defective.
Embodiment 7, preparation have the PET goods of antifogging coating
The aqueous solution with 100g 60% poly acrylic acid-poly acrylamide-2-methyl propane sulfonic acid (the calm and peaceful water treatment in Shandong company limited) (molecular-weight average is 2000Da), 1.5g polyfunctional group aziridine crosslinker CX100, the 100g particle diameter is that the titanium dioxide nano-particle water-sol (concentration is 20%) of 100nm mixes, in mixture, add the dilution of 1400g water, add the hydrochloric acid that a small amount of concentration is 1mol/L again, regulating the pH value is 2 to 4, adding 0.5g silane coupling agent TEOS (tetraethoxy) in addition stirs, with the line rod said mixture is coated the pet sheet face, in 120 ℃ of dryings 5 minutes, obtaining antifogging coating thickness was the PET goods of 1 μ m with PET.
Measuring physical properties:
Antifog property:＞1 minute (50 ℃ of water vapors), qualified;
Surface hardness: 2H;
Wear resistance (750g, 500r) g:0.01;
Cohesiveness:＞95%, qualified;
Water tolerance:＞300 hours, qualified;
Ultra-violet resistance:＞500 hours, qualified.
Embodiment 8, preparation have the PMMA goods of antifogging coating
With 100g 60% poly acrylic acid-poly acrylamide-2-methyl propane sulfonic acid (the calm and peaceful water treatment in Shandong company limited) (molecular-weight average is 2000), 1.5g aziridine crosslinker Sa100, the 10g particle diameter is the Nano particles of silicon dioxide water-sol (concentration is 50%) of 2nm, the 50g particle diameter is that the nano titania ionized water colloidal sol (concentration is 20%) of 100nm mixes, adding a small amount of concentration in said mixture is the hydrochloric acid of 1mol/L, adjustable value pH is 2 to 4, stir at adding 0.5g silane coupling agent TEOS (tetraethoxy), with the line rod mixture is coated the PMMA surface, in 120 ℃ of dryings 5 minutes, obtaining antifogging coating thickness was the PMMA goods of 2 μ m with PMMA.
Measuring physical properties:
Antifog property:＞1 minute (50 ℃ of water vapors), qualified;
Surface hardness: 2H;
Wear resistance (750g, 500r) g:0.01;
Cohesiveness:＞95%, qualified;
Water tolerance:＞300 hours, qualified;
Ultra-violet resistance:＞500 hours, qualified.
Embodiment 9, preparation have the PC goods of antifogging coating
Preparation poly acrylic acid-poly acrylamide-2-methyl propane sulfonic acid-polypropylene-base alkane ether hydroxyl sodium sulfonate: 10g vinylformic acid; 4g acrylamide-2-methyl propane sulfonic acid; 2g propenyl alkane ether hydroxyl sodium sulfonate is dissolved in the 25g water; be heated to 65 ℃; nitrogen protection adds 50 milligrams of ammonium persulphates down then; reactive polymeric 6 hours obtains molecular-weight average and is poly acrylic acid-poly acrylamide-2-methyl propane sulfonic acid-polypropylene-base alkane ether hydroxyl sodium sulfonate of 3000.
The aqueous solution with 100g 35% poly acrylic acid-poly acrylamide-2-methyl propane sulfonic acid-polypropylene-base alkane ether hydroxyl sodium sulfonate 35% (molecular-weight average is 3000Da), 2g polyfunctional group aziridine crosslinker SaC100, the 100g particle diameter is that the Nano particles of silicon dioxide water-sol (concentration is 15%) of 2nm mixes, adding a small amount of concentration in said mixture is the hydrochloric acid of 1mol/L, regulating the pH value is 2 to 4, adding 2g silane coupling agent TEOS (tetraethoxy) again stirs, with the line rod said mixture is coated the PC surface, in 100 ℃ of dryings 15 minutes, obtaining antifogging coating thickness was the PC goods of 2 μ m with PC.
Measuring physical properties:
Antifog property:＞1 minute (50 ℃ of water vapors), qualified;
Surface hardness: H;
Wear resistance (750g, 500r) g:0.02;
Cohesiveness:＜95%, defective;
Water tolerance:＞300 hours, defective;
Ultra-violet resistance:＜500 hours, defective.
Embodiment 10, preparation have the PET goods of antifogging coating
The aqueous solution with 100g 40% poly acrylic acid-poly propenyl alkane ether hydroxyl sodium sulfonate (Aldrich import reagent) (molecular-weight average is 7000), 1.5g polyfunctional group aziridine crosslinker CX100, the 10g particle diameter is that the Nano particles of silicon dioxide water-sol (concentration is 30%) of 8nm mixes, adding a small amount of concentration in said mixture is the hydrochloric acid of 1mol/L, regulating the pH value is 2 to 4, adding a small amount of 0.15g silane coupling agent KH560 (glycidyl ether propyl trimethoxy silicane) again stirs, with the line rod said mixture is coated the pet sheet face, in 120 ℃ of dryings 5 minutes, obtaining antifogging coating thickness was the PET goods of 3 μ m with PET.
Measuring physical properties:
Antifog property:＞1 minute (50 ℃ of water vapors), qualified;
Surface hardness: HB;
Wear resistance (750g, 500r) g:0.05;
Cohesiveness:＜95%, defective;
Water tolerance:＞300 hours, qualified;
Ultra-violet resistance:＞500 hours, qualified.
Embodiment 11, preparation have the PET goods of antifogging coating
The aqueous solution with 100g 30% polyacrylic acid (Aldrich import reagent) (molecular-weight average is 5000), 1.5g polyfunctional group aziridine crosslinker CX100, the 15g particle diameter is that the Nano particles of silicon dioxide water-sol (concentration is 20%) of 13nm mixes, adding a small amount of concentration in said mixture is the hydrochloric acid of 1mol/L, regulating the pH value is 2 to 4, adding a small amount of 0.25g silane coupling agent KH560 (glycidyl ether propyl trimethoxy silicane) again stirs, with the line rod said mixture is coated the pet sheet face, in 120 ℃ of dryings 5 minutes, obtaining antifogging coating thickness was the PET goods of 5 μ m with PET.
Measuring physical properties:
Antifog property:＞1 minute (50 ℃ of water vapors), qualified;
Surface hardness: HB;
Wear resistance (750g, 500r) g:0.6;
Cohesiveness:＜95%, defective;
Water tolerance:＜300 hours, defective;
Ultra-violet resistance:＜500 hours, defective.
Claims (9)
1. anti fogging coating composite, its composition comprises following component: the sour with acrylic or methacrylic of 0.5-58 mass parts is monomeric homopolymer or multipolymer, 0.05-6 the aziridine crosslinker of mass parts, the solvent of the inorganic nano-particle of 0.5-58 mass parts and 40-98 mass parts;
Described multipolymer is formed by acrylic or methacrylic acid mono and following at least a monomer polymerization: the compound shown in acrylamide-2-methyl-propyl sulfonic acid, Methacrylamide-2-methyl-propyl sulfonic acid, propenyl alkane ether hydroxyl sodium sulfonate or the formula I;
(formula I)
Among the formula I,
R
1Be H or CH
3
R
2Be C
N 'H
2n '+1N ' is the integer of 0-12, or (CH
2CH
2O)
N "N " is the integer of 1-20;
R
3Be SO
3H;
X is NH or NR
2R
3
N is the integer of 1-100, and m is the integer of 1-100;
Functional group's number in the described aziridine crosslinker is more than or equal to 2;
The molecular-weight average of described homopolymer or multipolymer is 500～50000Da.
2. anti fogging coating composite according to claim 1 is characterized in that: described inorganic nano-particle is an oxide nano-particles; The particle size range of described oxide nano-particles is 2-200nm; Described solvent is water and/or alcohol.
3. anti fogging coating composite according to claim 2 is characterized in that: described oxide nano-particles is Nano particles of silicon dioxide and/or titanium dioxide nano-particle.
4. according to arbitrary described anti fogging coating composite among the claim 1-3, it is characterized in that: the component of described anti fogging coating composite also comprises the catalyzer of 0.01-0.1 mass parts; Described catalyzer is mineral acid or organic acid.
5. anti fogging coating composite according to claim 4 is characterized in that: the component of described anti fogging coating composite also comprises following at least a: flow agent, coupling agent, oxidation inhibitor and film coalescence aid.
6. anti fogging coating composite according to claim 5 is characterized in that: described anti fogging coating composite is by forming for monomeric homopolymer or multipolymer, aziridine crosslinker, inorganic nano-particle, solvent, catalyzer and coupling agent with acrylic or methacrylic acid.
7. an antifogging coating is prepared by following method: arbitrary described anti fogging coating composite among the claim 1-6 is coated on the matrix, forms described antifogging coating after solidifying.
8. antifogging coating according to claim 7 is characterized in that: described matrix is resin, and the method for described coating is dip-coating, spraying, roller coating or brushing; Described solidified method is at 50-150 ℃ of dry 2-30min.
9. transparent resin product that is coated with claim 7 or 8 described antifogging coatings; The thickness of described antifogging coating is 0.2-100 μ m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100883189A CN101591494B (en) | 2009-07-03 | 2009-07-03 | Antifogging coating, special antifogging coating composition and antifogging product thereof |
Applications Claiming Priority (1)
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| WO2013089926A1 (en) * | 2011-12-15 | 2013-06-20 | 3M Innovative Properties Company | Anti-fog coating comprising aqueous polymeric dispersion, crosslinker & surfactant |
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| WO2013089926A1 (en) * | 2011-12-15 | 2013-06-20 | 3M Innovative Properties Company | Anti-fog coating comprising aqueous polymeric dispersion, crosslinker & surfactant |
| US10048408B2 (en) | 2011-12-15 | 2018-08-14 | 3M Innovative Properties Company | Anti-fog coating comprising aqueous polymeric dispersion, crosslinker and acid or salt of polyalkylene oxide |
| US10241237B2 (en) | 2011-12-15 | 2019-03-26 | 3M Innovative Properties Company | Anti-fog coating comprising aqueous polymeric dispersion, crosslinker and surfactant |
| WO2023111743A1 (en) * | 2021-12-15 | 2023-06-22 | SCG Chemicals Public Company Limited | Anti-fogging coating composition |
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