CN108239446A - Self-repairability coating composition, self-repairability coating, the protective film containing the coating and its application - Google Patents
Self-repairability coating composition, self-repairability coating, the protective film containing the coating and its application Download PDFInfo
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- CN108239446A CN108239446A CN201810053613.XA CN201810053613A CN108239446A CN 108239446 A CN108239446 A CN 108239446A CN 201810053613 A CN201810053613 A CN 201810053613A CN 108239446 A CN108239446 A CN 108239446A
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- 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
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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Abstract
The invention discloses a kind of self-repairability coating composition, including following component by weight：100 parts of fluorocarbon resin, 10 30 parts of polycarbonate glycol, 10 30 parts of Isocyanates curing agent；The number-average molecular weight of fluorocarbon resin is 1,000 50000, and glass transition temperature is 20~50 DEG C, and hydroxyl value is 30~100mgKOH/g, and acid value is 1~10mgKOH/g；Polycarbonate glycol is to be obtained by the di-alcohols of carbonic diester class and backbone c atoms number more than 2 through transesterification condensation reaction, and number-average molecular weight is 200 2000.The invention also discloses it is a kind of by the solution coating that the coating composition is configured in the self-repairability coating and the protective film comprising the coating that are obtained on base material and its application.The self-repairability coating composition of the present invention has both the self-regeneration characteristic of excellent weatherability and stabilization, especially suitable for long-term outdoor use.
Description
Technical field
The present invention relates to coating composition fields, and in particular to a kind of self-repairability coating composition, by the Coating material composition
Self-repairability coating, the protective film comprising the self-repairability coating and its application that object is prepared.
Background technology
Plastic material and wood quality etc. have excellent machine-shaping characteristic, and with glass, metal phase ratio, case hardness is low,
Scratch resistant performance is bad.Scratch resistant performance can be improved by the method for the coating varnish of surface spraying/brushing high crosslink density.
However, excessively high crosslink density also results in, coating is brittle and the binding force of base material declines.Once scratching, it is further development of
It crackle or even comes off, its defencive function will be lost.In daily production and living, the surface of passenger car is easily damaged by dust storm rubble
Wound, surface of vehicle paint easily form cut, small rut etc., have not only affected the overall beautiful of vehicle, but also increase and be further corroded
Risk.The building surface be made of marble, terrazzo and the workshop terrace for applying epoxy resin etc., are vulnerable to acid
Rain, sandstone and artificial influence cause surface to occur scratching and damaged, this not only influences specious, also increases maintenance
Cost.In addition, scratching the clast under coming off, it can also increase environmental problem.
In this context, different from common hard coat material, external force can be absorbed, realizes scratch, cut etc. self
The caoutchouc elasticity coating of repair function causes the flat 11- of the clear No. 63-86762 public affairs Reported , Te Open of extensive concern (such as Te Open of people
No. 42746 flat No. 11-43645 public affairs Reported of public affairs Reported , Te Open).
For example the public affairs Reported He Te Open 2006-328252 of Te Open 2006-124610 public affairs Reported propose one kind by polyester master
The polyurethane coating composition that agent and allophanic acid ester type curing agent are formed, realizes the work(for taking into account scratch resistance self-regeneration
Energy.
For another example No. 2007-31690 public affairs Reported of , Te Open propose it is a kind of containing short-side chain OH bases and long side chain OH bases third
The coating composition of olefin(e) acid resin, isocyanate curing agent and polycaprolactone polyol.
But polyester host agent is in UV resistant, high-temp resisting high-humidity resisting etc. Shortcomings, the item especially used outdoors
Under part, due to the hydrolysis of macromolecular chain so that the surface of coating composition tarnishes quickly, and self-regeneration characteristic is rapid
Decline and even disappear totally.On the other hand, using acrylic resin as the coating composition of main body, to realize that self-regeneration is special
Property and use polycaprolactone polyol compared with polyester system, the weatherability of coating entirety have as the soft segment part in structure
It is improved, but under long-term outdoor use, coating is caused to be reviewed one's lessons by oneself since the hydrolytic resistance of polycaprolactone polyol segment is insufficient
Multiple hydraulic performance decline is until lose.
Invention content
The technical problem to be solved in the present invention is to provide a kind of self-regeneration characteristic for having both excellent weatherability and stabilization,
The coating composition used especially suitable for long-term open air.
Another object of the present invention is to provide a kind of to be coated on reviewing one's lessons by oneself of being formed on base material by the coating composition solutions
Renaturation coating.
Another object of the present invention is to provide a kind of protective film comprising the self-repairability coating and its application.
In order to solve the above technical problem, the present invention provides a kind of self-repairability coating composition, including by weight
The following component of meter：
100 parts of fluorocarbon resin
10-30 parts of polycarbonate glycol
10-30 parts of Isocyanates curing agent.
In the present invention, term " fluorocarbon resin " is anti-by curing agent including fluorinated copolymer and by the fluorinated copolymer
The derivative that should be obtained.The fluorocarbon resin can be dissolved in common organic solvent, and containing in structure can crosslink
The hydroxyl group of reaction.
Preferably, fluorocarbon resin is by fluorinated olefin monomers, 'alpha '-olefin monomers and hydroxyl monomer is aggregated is obtained by the reaction
's.Wherein, the representative example of fluorinated olefin monomers includes tetrafluoroethene, 1,1,2- trifluoro-ethylene, vinylidene fluoride, 1,2-
Difluoroethylene, chlorotrifluoroethylene, hexafluoropropene；The representative example of 'alpha '-olefin monomers include isobutene, 2- Methyl-1-pentenes,
2- methyl-1s-hexene；The representative example of hydroxyl monomer includes 2- hydroxyethyl vinyl ethers, 3- hydroxypropyl vinyl
Ether, 2- hydroxypropyls vinyl ethers, -2 methyl-propyl vinyl ethers of 2- hydroxyls, 4- hydroxybutyl vinyl ethers, 5- Hydroxy pentyls
Vinyl ethers, 6- hydroxyl hexyls vinyl ethers, 2- hydroxyethyls allyl ether, 4- hydroxybutyl allyl ethers.
Preferably, fluorocarbon resin is by fluorinated olefin monomers, 'alpha '-olefin monomers, hydroxyl monomer and can be copolymerized therewith
Other monomers are aggregated obtained by the reaction.The representative example of fluorinated olefin monomers, 'alpha '-olefin monomers and hydroxyl monomer is as above
Described, other monomers include but not limited to the generating vinyl carboxylates esters such as vinylacetate, vinyl propionate；Dimethyl maleate, horse
Carry out the maleic acid diesters class such as diethyl phthalate；The dimethyl esters class such as dimethyl fumarate, diethyl fumarate；Methyl ethylene
The alkyl vinyls ethers such as ether, ethyl vinyl ether；Styrene, methyl acrylic ester.
The above-mentioned fluorocarbon resin with hydroxyl can pass through the modes such as well known polymerisation in solution, suspension polymerisation or emulsion polymerization
And it obtains.Its molecular weight is 1000~50000, preferably 6000~15000.Molecular weight is too low, the coating crosslink density of formation
Height, brittleness are big；Molecular weight is excessively high, dissolubility and the intersolubility decline with other resins.It is adjusted by forming, the glass of fluorocarbon resin
Glass transition temperature is -20~50 DEG C, preferably -10~40 DEG C.Glass transition temperature is too low, and the coating of formation is partially soft, machine
Tool performance is bad；Too high, coating is partially hard.Hydroxyl value is 30~100mgKOH/g, preferably 40~90mgKOH/g.Hydroxyl value is too low, film
Crosslink density it is low, film is partially soft；Hydroxyl value is excessively high, and film is partially hard partially crisp.Acid value is 1~10mgKOH/g, preferably 2~8mgKOH/g.
Acid value is too low, and the curing rate of film is excessively slow；Acid value is too high, and curing gel speed is too fast, and the weatherability of film declines.
The organic solvent for dissolving fluorocarbon resin can be ethyl acetate, butyl acetate, 2- butanone, propylene glycol monomethyl ether etc., excellent
It is selected as ethyl acetate or butyl acetate.
Commercially available typical case's fluorocarbon resin has Zeffle GK570, Zeffle GK550 (four fluorine-type, great Jin manufactures),
Lumiflon LF9100 (three fluorine-type, Asahi Glass manufacture), ZHM-2, ZHM-5 (Shanghai east fluorine) etc..From comprehensive physical property and supply property
From the aspect of, preferably Zeffle GK570.
In the present invention, term " polycarbonate glycol " refers to be more than by carbonic diester class and backbone c atoms number the two of 2
First alcohols, under the effect of the catalyst, the polymer obtained through transesterification condensation reaction, number-average molecular weight 200-2000.
It compares with polyether Glycols, polyester diol, polycaprolactone diols etc., polycarbonate glycol is due to its unique chemistry
Construction, shows excellent hydrolytic resistance, humidity resistance, ultraviolet resistance radiation characteristic.Gather made of polycarbonate glycol
Urethane material shows good mechanical performance, weatherability and abrasion performance.
Due to the polycarbonate glycol obtained using ethylene glycol as raw material, molecule chain rigidity is big and hydrolytic resistance is insufficient,
Therefore the present invention selects the di-alcohols that backbone c atoms number is more than 2.
Preferably, polycarbonate glycol be by the one or more of the di-alcohols that is selected from (a) in (b)
What carbonic diester class was obtained by transesterification condensation reaction：
(a) 1,3- propylene glycol, 2- methyl-1,3-propanediols, 2,2- dimethyl -1,3- propylene glycol (zinn glutaric alcohol NPG), 2-
The substitution such as ethyl -2- butyl -1,3- propylene glycol, 2,2- diethyl -1,3- propylene glycol, 2- amyl -2- propyl -1,3- propylene glycol 1,
3-propanediol class；1,4- butanediols, 1,5- pentanediols, 1,6-HD, 1,7- heptandiols, 1,8- ethohexadiols, 1,9- nonanediols,
The straight diols classes such as 1,10- decanediols, 11 carbon glycol of 1,11-, 12 carbon glycol of 1,12-；Diglycol (DEG), two
The oxygen-containing main chain glycols such as contracting triethylene glycol, tetraethylene-glycol, polyethylene glycol, polytetramethylene glycol；2- ethyls -1,6-HD,
3- methyl-1s, 5- pentanediols etc. replace glycols；1,4- cyclohexanediols, 1,4- dihydroxy methylenecyclohexane, (the 4- hydroxyls of 2,2- bis-
Butylcyclohexane base) the fatty ring class such as propane；The alcamines such as diethanol amine, N methyldiethanol amine；
Consider that di-alcohols is preferred from the synthesis physical property of the reactivity of raw material, supply and final polycarbonate glycol
For one kind in 1,3- propylene glycol, 2- methyl-1,3-propanediols, 1,4- butanediols, 1,5- pentanediols, 1,6-HD or more
Kind.
(b) dialkyl carbonates, carbonic acid diallyl esters, dipheryl carbonate base ester class, cyclic carbonates etc.；
From the viewpoint of reactivity, carbonic diester class is preferably dimethyl carbonate, diethyl carbonate, diphenyl carbonate or carbon
Vinyl acetate；From cost and supply, more preferably diethyl carbonate or ethylene carbonate, further preferably carbonic acid two
Ethyl ester.
The polycarbonate glycol of the present invention, is passed through using di-alcohols and carbonic diester class as raw material, under high-temperature low-pressure
Transesterification condensation reaction obtains.The catalyst used in reaction is inorganic metal salt or organic metal salt, and residual quantity should
When stringent management and control, to be advisable in below 100ppm, best 50ppm is hereinafter, it is preferred that below 10ppm；Residual is excessive, influences poly- carbonic acid
The further polyurethane-reinforcement reaction of ester dihydric alcohol, so as to influence the final performance of product.
Above-mentioned metallic salt, including second major elements such as first major element such as lithium, sodium, magnesium, calcium, titanium, zirconium, hafnium etc.
The metallic salt of transition metal and cobalt, zinc, aluminium, germanium, tin, lead, antimony, bismuth etc.；The preferably metallic salt of lithium, sodium, magnesium etc.,
Including its hydroxide, chloride, bromide, iodide, acetate, formates, benzoate, mesylate, methylbenzene
Sulfonate, carbonate, methoxyl group salt are (for example, MOCH3), ethyoxyl salt (MOC2H5) etc..
The polycarbonate glycol of the present invention is manufactured, using the ingredient proportion of di-alcohols excess, it is assumed that di-alcohols 1
Mole, then the lower limit of carbonic diester class is 0.35 mole, preferably 0.5 mole, preferably 0.6 mole；The upper limit is 1 mole, excellent
It is selected as 0.99 mole, more preferably 0.98 mole.The molal quantity of carbonic diester class then leads to the makrolon two of gained close to 1
First alcohol molecular weight is higher；The upper limit causes the content of polycarbonate glycol molecule chain end non-hydroxyl group to increase more than 1 mole
It is more, in production rate of charge is determined according to the theoretical molecular weight of product.
Reaction kettle is preferably equipped with reflux condensate device and decompressor.The temperature of ester exchange reaction controls
Preferably, further for 190 DEG C hereinafter, preferably less than 180 DEG C.If temperature is excessively high, the final color and luster of product is deepened, and influences end article
Appearance；Temperature is too low, and the reaction time is long, and the impurity of molecule chain end non-hydroxyl increases.Because ester exchange reaction is balance
Reaction, low boiling point monohydric alcohol, glycols are detached from system so that reaction is smoothed out.The later stage is reacted, by decompression, is improved anti-
The carry out degree answered.The pressure of reaction terminating is advisable for below 10Kpa, and preferably 5KPa is hereinafter, preferably below 1Kpa.
Reaction time depending on actual conditions, according to the presence or absence of difference, catalyst for using raw material and type.On reaction way
In, reaction can be detected with suitable means carries out degree.Reaction time was usually advisable with less than 50 hours, and preferably 20 is small
When within, within preferably 10 hours.Catalyst deactivator can be also added in when necessary, such as inorganic phosphate, phosphorous acid, phosphoric acid ester
Deng forced termination reaction.
Excessive di-alcohols, carbonic diester class are removed by way of vacuum distillation or thin-film distillation and may be generated
The impurities such as cyclic compound.
The polycarbonate glycol of the present invention, molecule chain end is hydroxyl, but according to used carbonic diester class
Difference, the also impurity there are non-hydroxyl end, for example end is methoxyl group, the impurity of ethyoxyl, phenoxy group, passes through NMR
And the analysis means such as high performance liquid chromatography can solve it is bright.The content of impurity should be controlled in 5% (weight) hereinafter, it is preferred that 3%
Hereinafter, more preferable 1% hereinafter, to ensure that polycarbonate glycol is entered as effective segment in molecular structure, fully send out
Wave its mechanical strength and the performances such as heat-resisting.
The molecular weight of the polycarbonate glycol of the present invention is 200-2000, preferably 500-1000.If molecular weight is too low,
The hardness of the material formed is bigger than normal, and elasticity is insufficient；Molecular weight is too big, and viscosity is excessive and the intersolubility of his resin declines, and causes
Mechanicalness is deteriorated.Molecular weight distribution mw/mn is preferably 1.5-3.5, more preferably 1.8-3.0.If molecular weight distribution is narrow, formed
Resin elasticity it is big, partially firmly；Wide, then final resin is partially soft, and weatherability and mechanical performance are low.
The melting temperature lower limit of the polycarbonate glycol of the present invention is -20 DEG C, preferably -15 DEG C, more preferably -10
℃.Tm is too low, and the final physical property of paint composite is partially soft, and mechanical performance is bad.Tm is excessive, and product appearance is half flowable state or wax
Shape declines with the intersolubility of his resin.
In the present invention, term " Isocyanates curing agent " refers to containing the different of two or more isocyanate groups
Cyanate or Polyisocyanate esters compound.For example, Isocyanates curing agent is aliphatic diisocyanate, it is representative real
Example includes 1,4- tetramethylene diisocyanates, 1,5- pentamethylene diisocyanates, 1,6- hexamethylene diisocyanates, 2,
2,4- trimethyl -1,6- hexamethylene diisocyanates, 2,4,4- trimethyl -1,6- hexamethylene diisocyanates, dimeric dibasic acid
Diisocyanate；
Alternatively, Isocyanates curing agent is alicyclic diisocyanate, representative example includes Isosorbide-5-Nitrae-cyclohexyl two
Isocyanates, isophorone diisocyanate, 1- methyl -2,4- cyclohexyls diisocyanate, 1- methyl -2,6- cyclohexyls
Diisocyanate, 4,4- cyclohexyls methane diisocyanate, 1,3- bis- (isocyanates methylene) hexamethylene, 1,4- bis-
(isocyanates methylene) hexamethylene；
Alternatively, Isocyanates curing agent is aromatic isocyanate, representative example includes 2,4- diisocyanate ester groups
Toluene (TDI), 2,6- diisocyanate ester groups toluene, diisocyanate ester group benzene, to diisocyanate ester group benzene, 4,4- xenyls two
Isocyanates, 4,4- methyl diphenylene diisocyanates, 1,3- benzhydryls diisocyanate (XDI), dialkyl group diphenyl methane
Diisocyanate, tetraalkyl methyl diphenylene diisocyanate, 1,5- naphthalene diisocyanates, 3,3- dimethyl -4,4- biphenyl
Group diisocyanate.
In the present invention, Isocyanates curing agent can also add for what is obtained by raw material of above-mentioned diisocyanate compound
It is molded polyisocyanate, biuret form polyisocyanate, allophanic acid ester type polyisocyanate or the poly- isocyanide of isocyanurate type
Acid esters.Supply from weatherability, adjusting physical property and product angularly considers that Isocyanates curing agent is preferably 1,
The isocyanurate type derivative (i.e. HDI trimer) of 6- hexamethylene diisocyanates (HDI).Commercial product is listed below,
Such as Asahi Chemical Industry TPA100, TPA90SB, TKA100, Desmodur N3300, N3390, Tosoh HX, the HL series of Baeyer, three wells
Chemical D-170 etc., preferably TPA100 and Desmodur N3390.
The present invention coating composition in, fluorocarbon resin, polycarbonate glycol, Isocyanates curing agent three ratio
Example is 100/10-30/10-30, if polycarbonate glycol amount is insufficient, coating is partially hard, and weather resistance is good, but under self-repairability
Drop；And polycarbonate glycol it is excessive when, coating is partially soft, and self-repair type can be good, but intersolubility declines, and appearance albefaction is bad.
In the coating composition of the present invention, fluorocarbon resin is formed as main resin, polycarbonate glycol as chain extender
3 D stereo reticular structure.Wherein, fluorocarbon resin provides hydroxyl OH associated with friendship with polycarbonate glycol, and isocyanates is solid
The molar ratio NCO/OH of the NCO functional groups of agent offer curing reaction, NCO functional groups and hydroxyl OH are 1.0-3.0, preferably
1.1-2.5 more preferably 1.2-2.0；If NCO/OH is less than 1, crosslinking is insufficient, and self-repairability is poor, the binding force with base material
Deficiency, weatherability are bad；If more than 3, the coating formed is partially hard, and self-healing properties decline.
Aforementioned three kinds of required components when in use, need to be dissolved into appropriate organic solvent by the coating composition of the present invention
In, its viscosity is adjusted, suitable coating solution is made.Ethyl acetate, butyl acetate, isobutyl acetate etc. can be used in organic solvent
Esters, the ketones such as acetone, 2- butanone, methyl iso-butyl ketone (MIBK), the ethers such as tetrahydrofuran, propylene glycol monomethyl ether and toluene, diformazan
The arenes such as benzene.Consider from technique and cost angle, pay the utmost attention to ethyl acetate or butyl acetate.Consolidating in coating solution contains
Amount concentration is advisable with 20-70%, and viscosity is advisable with 200-2000mPas, the concentration for being coated with solution can be done according to coating method suitable
When adjustment.During low concentration, viscosity is low, is easy to construct, and suitable for spraying, but VOC emission is on the high side；During high concentration, viscosity is high, suitable
Roller coating, brushing, but excessively high viscosity can influence appearance of coat, increase the difficulty of construction.
To improve application property, obtaining good appearance of coat, levelling agent can be added in when necessary, in coating composition, is disappeared
The auxiliary agents such as infusion, wetting agent.It can also consider to add in the additives such as commercially available ultraviolet absorber, UV stabilizer, antioxidant,
To further improve the weatherability of coating.To improve the rheological behavior of mechanical performance and coating composition, inorganic fill out can be added in
Material, such as silica, titanium dioxide, zirconium dioxide, alundum (Al2O3), mica, talcum powder, calcium carbonate, barium sulfate, magnesium sulfate
Deng size is advisable with sub-micron, nanoscale, and shape is spherical shape, sheet, needle-shaped etc. is advisable.
The present invention also provides a kind of self-repairability coating, be by above-mentioned coating solution coating on suitable base material,
It is obtained after dry cure.The coating can protect base material, have the self-regeneration characteristic of wound cut.Coating layer thickness with 10~
20 microns are advisable, preferably 20~30 microns, more preferably 30~40 microns.If thickness is excessively thin, overweight mechanical external force shape
Into cut coating will be caused integrally to be broken, it is difficult to realize self-regeneration；It is blocked up, though self-regeneration characteristic is good, coating process
Difficulty, causes bad order at the defects of being easily formed bubble.
Above-mentioned base material, i.e., practical construction surface, can be metal surface, wood surface, concrete surface, painted surface,
High molecule plastic surface etc..Before coating, substrate surface will be through processing such as over cleaning, degreasing, dedusting, polishings.Particularly, to modeling
Expect class, polymeric membrane class base material, such as polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate (PET), poly- ammonia
Ester thermoplastic elastomer (TPU), acryl resin, polysulfones, polyphenylene sulfide, polyether-ether-ketone, polyimides, Kynoar etc., it is right
Surface will carry out the scorching processing of sided corona treatment, corona treatment, fire, primary coat primer processing etc., with increase coating and base material it
Between adherence.
After coating solution is made in coating composition, according to viscosity and substrate property, directly coating or indirect may be used
Coating method.Spraying, roller coating, brushing are specifically included, scraper, silk stick, anilox roll, micro- anilox roll, silk-screen printing etc. can be used
Mode.After coating, by placing or heating baking naturally to remove solvent, steady temperature or gradient liter may be used in when baking
Warm mode, the preference temperature of baking are determined according to practical solvent composition and base material used.High-temperature baking can shorten baking
Time so that coating reacts rapidly and shows self-healing properties, but may be decreased its adherence with base material；And low-temperature bake
It then can extend the reaction time, increase the adherence of coating and base material and improve appearance, but the construction time can be increased, so as to reduce life
Produce efficiency.
The present invention also provides a kind of protective film, including polymeric membrane and it is attached to the above-mentioned coating on polymeric membrane surface
Obtained from end article or semi-finished product.For semi-finished product, commercially available pressure sensitive adhesive etc. can be in addition coated at the back side of polymeric membrane,
To be bonded with affixed object.
After the toasted removal solvent of coating, easily removing film is bonded the continuous production, it can be achieved that roll-to-roll with release film etc..Institute
Ripening at low temperature mode may be used in the composite membrane obtained, completes the curing reaction of coating composition.Curing temperature is with 30~60 DEG C
Preferably, the time was advisable with 24 hours~1 week.
The self-repairability coating of the present invention and the protective film containing the coating, can be applied to passenger car, household electrical appliances, furniture, build
Build object surface etc..
The beneficial effects of the invention are as follows：
The self-repairability coating composition of the present invention has both the self-regeneration characteristic of excellent weatherability and stabilization, especially
Suitable for long-term outdoor use.
The present invention self-repairability coating composition, can be formed by modes such as spraying, roller coating self-repairability coating or
Protective film with self-repairability is formed by roll-to-roll mode, the adherence of coating and base material is good, the coating and contains
The protective film of the coating can be widely applied to the different field such as passenger car, household electrical appliances, furniture, building surface.
Specific embodiment
With reference to specific embodiment, the invention will be further described, so that those skilled in the art can be preferably
Understand the present invention and can be practiced, but illustrated embodiment is not as a limitation of the invention.
1. polycarbonate synthesis dihydric alcohol
Synthesis example 1
In 1000 milliliters of three mouthfuls of volumetric flasks for being equipped with blender, thermometer and condenser pipe, 2- methyl-1s are added in, 3- the third two
Alcohol (369.5g, 4.1mol), diethyl carbonate (366.2g, 3.1mol), 20% ethanol solution of catalyst sodium ethoxide (0.12g,
0.35mmol).Under nitrogen atmosphere, the lasting stirring of 100-120 DEG C of temperature is kept, distills out coproduct ethanol.When the steaming of ethyl alcohol
When output reaches the 30-40% of theoretical value, 170 DEG C are warming up to 4-10 DEG C/h of speed, keeps the temperature to ethanol distillation
It completes.Next, being kept for 170 DEG C, 1.3kPa is gradually decompressed in reaction unit, sustained response carries out further anti-for 2 hours
Should, finally obtain the polycarbonate glycol that number-average molecular weight is about 500, molecular weight distribution 1.8, Tm~-5 DEG C, purity>
99%, it is denoted as A1.
Synthesis example 2
In 1000 milliliters of three mouthfuls of volumetric flasks for being equipped with blender, thermometer and condenser pipe, 1,5-PD is added in
(244.75g, 2.35mol) and 1,6- hexylene glycol (277.72g, 2.35mol), diethyl carbonate (366.2g, 3.7mol), catalysis
20% ethanol solution of agent sodium ethoxide (0.14g, 0.41mmol).Under nitrogen atmosphere, the lasting stirring of 100-120 DEG C of temperature is kept,
Distill out the ethyl alcohol of generation.When the amount of steaming of ethyl alcohol reaches the 30-40% of theoretical value, heated up with 4-10 DEG C/h of speed
To 170 DEG C, the temperature to ethanol distillation is kept to complete.Next, being kept for 170 DEG C, 1.3kPa is gradually decompressed in reaction unit,
Sustained response is further reacted for 2 hours, obtains the polycarbonate glycol that number-average molecular weight is about 500, molecular weight point
Cloth 1.9, Tm~-10 DEG C, purity>99%, it is denoted as A2.
Synthesis example 3
Using the 2- methyl-1s of 315.4g, 3-propanediol (3.5mol), other conditions obtain several equal molecules with synthesis example 1
The polycarbonate glycol of amount about 1000, molecular weight distribution 2.0, Tm~-7 DEG C, purity>99%, it is denoted as A3.
Synthesis example 4
Using the 2- methyl-1s of 305.8g, 3-propanediol (3.2mol), other conditions obtain several equal molecules with synthesis example 1
The polycarbonate glycol of amount about 2500, molecular weight distribution 2.3, Tm~-12 DEG C, purity>99%, it is denoted as A4.
2. coating composition solutions are configured
Coating composition solutions A
Commercially available 100 parts of fluorocarbon resin varnish GK570 (big King Company, solid content 65%, hydroxyl value 40, acid value 6.5), the present invention
20 parts of polycarbonate glycol (A1), 25 parts of Isocyanates curing agent TPA100 (Asahi Chemical Industry), 75 parts of ethyl acetate solvent,
It is uniformly mixing to obtain the coating composition solutions of solid content about 50%.Viscosity is about 25 DEG C of 400cps@.
Coating composition solutions B
Commercially available 100 parts of fluorocarbon resin varnish GK570 (big King Company, solid content 65%, hydroxyl value 40, acid value 6.5), the present invention
20 parts of polycarbonate glycol (A2), 25 parts of Isocyanates curing agent TPA100 (Asahi Chemical Industry), 75 parts of ethyl acetate solvent,
It is uniformly mixing to obtain the coating composition solutions of solid content about 50%.Viscosity is about 25 DEG C of 360cps@.
Coating composition solutions C
Commercially available 100 parts of fluorocarbon resin varnish GK570 (big King Company, solid content 65%, hydroxyl value 40, acid value 6.5), the present invention
20 parts of polycarbonate glycol (A3), 16 parts of Isocyanates curing agent TPA100 (Asahi Chemical Industry), 66 parts of ethyl acetate solvent,
It is uniformly mixing to obtain the coating composition solutions of solid content about 50%.Viscosity is about 25 DEG C of 500cps@.
Coating composition solutions D
Commercially available 100 parts of fluorocarbon resin varnish GK570 (big King Company, solid content 65%, hydroxyl value 40, acid value 6.5), isocyanic acid
10 parts of esters curing agent TPA100 (Asahi Chemical Industry), 40 parts of ethyl acetate solvent are uniformly mixing to obtain the coating of solid content about 50%
Composition solution.Viscosity is about 25 DEG C of 400cps@.
Coating composition solutions E
Commercially available 100 parts of fluorocarbon resin varnish GK570 (big King Company, solid content 65%, hydroxyl value 40, acid value 6.5), the present invention
20 parts of polycarbonate glycol (A4), 13 parts of Isocyanates curing agent TPA100 (Asahi Chemical Industry), 63 parts of ethyl acetate solvent,
It is uniformly mixing to obtain the coating composition solutions of solid content about 50%.Viscosity is about 25 DEG C of 850cps@.
3. prepare self-repairability coating
Coating composition solutions A~E is taken, carries out following operate：
1) parkerized stainless steel surface (abbreviation base material 1), 80 DEG C of * 3min dryings, further 150 DEG C of * are sprayed to
30min is thermally treated resulting in uniform coating, and thickness is about 30 microns；
2) surface (abbreviation base material 2) for the 75 microns of PET films crossed with blade coating to sided corona treatment, 80 DEG C of * 3min+120
After DEG C * 3min drying, 40 DEG C of * 3day maturation process；
3) with the surface (abbreviation base material 3) of 150 microns of TPU membranes of blade coating to non-sided corona treatment, 80 DEG C of * 3min+120
After DEG C * 3min drying, the PET release films pressurizing attaching (room temperature, 2 kgfs, 5min) with 50 micron thickness, 40 DEG C of * 3day are ripe
Change is handled；
4) in the layer upper surface with blade coating coating fluid to 50 microns of PET release films, 80 DEG C of * 3min+120 DEG C * 3min
After drying, be bonded with PVC film (abbreviation base material 4) hot pressing (40 DEG C, 2 kgfs, 5min), 40 DEG C of * 3day maturation process.
After aforesaid operations, 10 kinds of coating samples are obtained, are respectively designated as Examples 1 to 8 and comparative example 1~2, specifically
As shown in table 1.
4. performance detection
The coating of Example 1~8 and comparative example 1~2, it is carried out respectively self-repairability, adherence, optical property and
Case hardness is tested, and acquired results are as shown in table 1.
Self-repairability is tested：Commercially available brass brush, loading weigh 1 kilogram, and in coat side after reciprocal 10 times, observation is at room temperature
No recovery, while 50 DEG C of warm water are contacted, the time (unit, second) used in record recovery.
Adherence is tested：It is good for adherence with hundred Gree test methods, 100/100 with reference to coating testing standard.80-
90/100 is bad for adherence.
Optical performance test：Range estimation.
Case hardness is tested：With reference to coating testing standard, tested using pencil hardness instrument, loading 750g.
The performance test results of the coating sample of 1 Examples 1 to 8 of table and comparative example 1~2
From table 1 it follows that by the coating composition (embodiment 1-8) of the present invention, show that good selfreparing is special
Property, it is good with the adherence of various typical substrates, and appearance transparent.And polycarbonate glycol is not added in coating composition,
The higher varnish of hardness can be formed, is declined with the adherence of base material, no self-healing properties (comparative example 1).Using high-molecular-weight poly
Carbonic acid dihydric alcohol, the intersolubility of system decline, and self-healing properties are excellent, but transparency declines, bad order (comparative example 2).
To sum up, self-repairability coating of the invention, the coating and protection containing the coating good with the adherence of base material
Film can be widely applied to the different field such as passenger car, household electrical appliances, furniture, building surface.
Embodiment described above is only to absolutely prove preferred embodiment that is of the invention and being lifted, protection model of the invention
It encloses without being limited thereto.The equivalent substitute or transformation that those skilled in the art are made on the basis of the present invention, in the present invention
Protection domain within.Protection scope of the present invention is subject to claims.
Claims (10)
1. self-repairability coating composition, which is characterized in that including following component by weight：
100 parts of fluorocarbon resin
10-30 parts of polycarbonate glycol
10-30 parts of Isocyanates curing agent；
Wherein, the number-average molecular weight of the fluorocarbon resin is 1000-50000, and glass transition temperature is -20~50 DEG C, hydroxyl value
For 30~100mgKOH/g, acid value is 1~10mgKOH/g；
The polycarbonate glycol is to be condensed by carbonic diester class and di-alcohols of the backbone c atoms number more than 2 through transesterification
It is obtained by the reaction, number-average molecular weight 200-2000.
2. self-repairability coating composition as described in claim 1, which is characterized in that the fluorocarbon resin is by being selected from (a)
In fluorinated olefin monomers, 'alpha '-olefin monomers in (b) and the hydroxyl monomer in (c) is aggregated is obtained by the reaction
's；
(a) tetrafluoroethene, 1,1,2- trifluoro-ethylenes, 1,1- difluoroethylenes, 1,2- difluoroethylenes, chlorotrifluoroethylene, hexafluoropropene；
(b) isobutene, 2- Methyl-1-pentenes, 2- methyl-1s-hexene；
(c) 2- hydroxyethyl vinyl ethers, 3- hydroxypropyls vinyl ethers, 2- hydroxypropyls vinyl ethers, -2 methyl of 2- hydroxyls
Propyl vinyl ether, 4- hydroxybutyl vinyl ethers, 5- Hydroxy pentyls vinyl ethers, 6- hydroxyl hexyls vinyl ethers, 2- hydroxyls
Ethyl allyl ether, 4- hydroxybutyl allyl ethers.
3. self-repairability coating composition as described in claim 1, which is characterized in that the fluorocarbon resin is by being selected from (a)
In fluorinated olefin monomers, the 'alpha '-olefin monomers in (b), the hydroxyl monomer in (c) and other in (d)
Monomer is aggregated obtained by the reaction；
(a) tetrafluoroethene, 1,1,2- trifluoro-ethylenes, 1,1- difluoroethylenes, 1,2- difluoroethylenes, chlorotrifluoroethylene, hexafluoropropene；
(b) isobutene, 2- Methyl-1-pentenes, 2- methyl-1s-hexene；
(c) 2- hydroxyethyl vinyl ethers, 3- hydroxypropyls vinyl ethers, 2- hydroxypropyls vinyl ethers, -2 methyl of 2- hydroxyls
Propyl vinyl ether, 4- hydroxybutyl vinyl ethers, 5- Hydroxy pentyls vinyl ethers, 6- hydroxyl hexyls vinyl ethers, 2- hydroxyls
Ethyl allyl ether, 4- hydroxybutyl allyl ethers；
(d) generating vinyl carboxylate esters, maleic acid diester class, dimethyl ester class, alkyl vinyl ethers, styrene, metering system
Esters of gallic acid.
4. self-repairability coating composition as described in claim 1, which is characterized in that the polycarbonate glycol is by selecting
What one or more carbonic diester classes in (f) of the di-alcohols from (e) were obtained by transesterification condensation reaction；
(e) 1,3- propylene glycol, 2- methyl-1,3-propanediols, 2,2- dimethyl -1,3- propylene glycol, 2- ethyl -2- butyl -1,3-
Propylene glycol, 2,2- diethyl -1,3- propylene glycol, 2- amyl -2- propyl -1,3- propylene glycol, 1,4- butanediols, 1,5- pentanediols,
1,6-HD, 1,7- heptandiols, 1,8- ethohexadiols, 1,9- nonanediols, 1,10- decanediols, 11 carbon glycol of 1,11-, 1,12-
12 carbon glycol, diglycol, triethylene-glycol, tetraethylene-glycol, polyethylene glycol, polytetramethylene glycol, 2- ethyl -1,
6- hexylene glycols, 3- methyl-1s, 5- pentanediols, 1,4- cyclohexanediols, 1,4- dihydroxy methylenecyclohexane, (the 4- hydroxyls of 2,2- bis-
Cyclohexyl) propane, diethanol amine, N methyldiethanol amine；
(f) dialkyl carbonates, carbonic acid diallyl esters, dipheryl carbonate base ester class, cyclic carbonates.
5. self-repairability coating composition as described in claim 1, which is characterized in that in the polycarbonate glycol, point
The content of the impurity of subchain end non-hydroxyl is less than 5% (weight).
6. self-repairability coating composition as described in claim 1, which is characterized in that the Isocyanates curing agent choosing
From：
1,4- tetramethylene diisocyanates, 1,5- pentamethylene diisocyanates, 1,6- hexamethylene diisocyanates, 2,2,
4- trimethyl -1,6- hexamethylene diisocyanates, 2,4,4- trimethyl -1,6- hexamethylene diisocyanates, dimeric dibasic acid two
Isocyanates, 1,4- cyclohexyls diisocyanate, isophorone diisocyanate, two isocyanide of 1- methyl -2,4- cyclohexyls
Acid esters, 1- methyl -2,6- cyclohexyls diisocyanate, 4,4- cyclohexyls methane diisocyanate, bis- (isocyanates of 1,3-
Methylene) hexamethylene, 1,4- bis- (isocyanates methylene) hexamethylene, 2,4- diisocyanate ester groups toluene, 2,6- bis- be different
Cyanic acid ester group toluene, diisocyanate ester group benzene, to diisocyanate ester group benzene, 4,4- biphenylene diisocyanates, 4,4- hexichol
Dicyclohexylmethane diisocyanate, 1,3- benzhydryls diisocyanate, dialkyl group methyl diphenylene diisocyanate, tetraalkyl diphenyl
Methane diisocyanate, 1,5- naphthalene diisocyanates, 3,3- dimethyl -4,4- biphenylene diisocyanates；With
Additive poly isocyanates, biuret form polyisocyanate, the poly- isocyanide of allophanic acid ester type obtained using them as raw material
Acid esters, isocyanurate type polyisocyanate.
7. self-repairability coating composition as described in claim 1, which is characterized in that in the self-repairability coating composition
Also include auxiliary agent.
8. a kind of self-repairability coating, which is characterized in that be configured by claim 1-7 any one of them coating compositions
Solution coating is in obtaining on base material.
9. a kind of protective film, which is characterized in that including polymeric membrane and be coated on the polymeric membrane surface as right will
Seek the self-repairability coating described in 8.
10. protective film described in self-repairability coating according to any one of claims 8 or claim 9 passenger car, household electrical appliances, furniture with
And the application of building surface.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110452587A (en) * | 2019-08-27 | 2019-11-15 | 广西科技大学 | A kind of high-weatherability fluorocarbon coating and preparation method |
| CN110872467A (en) * | 2018-09-03 | 2020-03-10 | 富士施乐株式会社 | Surface-protective resin member, laminated resin member, and liquid set |
| CN113583559A (en) * | 2021-08-13 | 2021-11-02 | 江苏图研新材料科技有限公司 | Self-repairing coating paint, preparation method thereof, coating, film and device |
| CN113912819A (en) * | 2021-09-28 | 2022-01-11 | 广东粤港澳大湾区黄埔材料研究院 | Polyurethane material and preparation method and application thereof |
| CN114573986A (en) * | 2020-12-01 | 2022-06-03 | 中国科学院化学研究所 | 3D printing part capable of being completely degraded and recycled, and preparation method and application thereof |
| CN117659339A (en) * | 2024-01-31 | 2024-03-08 | 中天科盛科技股份有限公司 | Self-repairing yellowing-resistant high-transparency aliphatic polyurethane elastomer and preparation method thereof |
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| CN104072713A (en) * | 2013-03-26 | 2014-10-01 | 富士施乐株式会社 | Resin material and protective film |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104072713A (en) * | 2013-03-26 | 2014-10-01 | 富士施乐株式会社 | Resin material and protective film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110872467A (en) * | 2018-09-03 | 2020-03-10 | 富士施乐株式会社 | Surface-protective resin member, laminated resin member, and liquid set |
| CN110452587A (en) * | 2019-08-27 | 2019-11-15 | 广西科技大学 | A kind of high-weatherability fluorocarbon coating and preparation method |
| CN110452587B (en) * | 2019-08-27 | 2022-04-01 | 广西科技大学 | High-weather-resistance fluorocarbon coating and preparation method thereof |
| CN114573986A (en) * | 2020-12-01 | 2022-06-03 | 中国科学院化学研究所 | 3D printing part capable of being completely degraded and recycled, and preparation method and application thereof |
| CN114573986B (en) * | 2020-12-01 | 2023-04-07 | 中国科学院化学研究所 | 3D printing part capable of being completely degraded and recycled, and preparation method and application thereof |
| CN113583559A (en) * | 2021-08-13 | 2021-11-02 | 江苏图研新材料科技有限公司 | Self-repairing coating paint, preparation method thereof, coating, film and device |
| CN113583559B (en) * | 2021-08-13 | 2022-07-29 | 江苏图研新材料科技有限公司 | Self-repairing coating paint, preparation method thereof, coating, film and device |
| CN113912819A (en) * | 2021-09-28 | 2022-01-11 | 广东粤港澳大湾区黄埔材料研究院 | Polyurethane material and preparation method and application thereof |
| CN117659339A (en) * | 2024-01-31 | 2024-03-08 | 中天科盛科技股份有限公司 | Self-repairing yellowing-resistant high-transparency aliphatic polyurethane elastomer and preparation method thereof |
| CN117659339B (en) * | 2024-01-31 | 2024-04-12 | 中天科盛科技股份有限公司 | Self-repairing yellowing-resistant high-transparency aliphatic polyurethane elastomer and preparation method thereof |
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Effective date of registration: 20221223 Address after: No.66 Jiefang Road, Lishi Town, Zhenjiang District, Shaoguan City, Guangdong Province, 512000 Patentee after: Zhang Jinbo Address before: Room 201, Building 13, North West Area, Suzhou Nanotown, No. 99, Jinjihu Avenue, Suzhou Industrial Park, Jiangsu Province, 215000 Patentee before: SUZHOU ZHONGSHI HUIHUA SYNTHETIC MATERIAL Co.,Ltd. |