CN110387187A - The polyurethane water-proof paint of one pack system - Google Patents
The polyurethane water-proof paint of one pack system Download PDFInfo
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- CN110387187A CN110387187A CN201810353238.0A CN201810353238A CN110387187A CN 110387187 A CN110387187 A CN 110387187A CN 201810353238 A CN201810353238 A CN 201810353238A CN 110387187 A CN110387187 A CN 110387187A
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- China
- Prior art keywords
- polyurethane water
- weight
- polyurethane
- proof
- molecular weight
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Classifications
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
- E04D13/00—Special arrangements or devices in connection with roof coverings; Protection against birds; Roof drainage; Sky-lights
- E04D13/16—Insulating devices or arrangements in so far as the roof covering is concerned, e.g. characterised by the material or composition of the roof insulating material or its integration in the roof structure
Abstract
The present invention relates to a kind of Moisture Curing Polyurethane Waterproof Coatings of one pack system, the film and waterproof system formed by the coating.The polyurethane water-proof paint includes :-at least one the polyurethane prepolymer formed by polyol component and toluene di-isocyanate(TDI), with-at least one aldimine type latent curing agent, wherein the polyol component includes from the trihydroxylic alcohol greater than 50 to 90 weight % and from 10 to the dihydric alcohol less than 50 weight %, and the average molecular weight of the trihydroxylic alcohol is 3000-6000g/mol and the average molecular weight of the dihydric alcohol is 1000-4000g/mol.
Description
Invention field
The present invention relates to a kind of moisture curable polyurethane water-proof paint of one pack system, the film and waterproofs that formed by the coating
System.Particularly, polyurethane water-proof paint of the invention be one pack system, low temperature applicable moisture curable coating.
Background of invention
The waterproof membrane that liquid applies is known.In roofing application, they are used as the substitute of prefabricated film film,
Offer is more easily applied, especially task in the case where complicated roof geometry and for renovation, has been provided
The flexible seamless roofing coating of substrate is adhered to entirely.
It is often reaction type polyurethane composition that the liquid of the prior art, which applies waterproof membrane, is formulated as one pack system or double groups
Fission system, is also known respectively as single part or double sectional interests.Bicomponent system needs special mixing apparatus using more complicated
Two kinds of components are measured with appropriate, and single-component system is then easy to apply.Many polyurethane water-proofs are provided in the prior art to apply
The solution of material.
CN105315878A discloses a kind of solvent free mono-composition poyurethane water-proof paint, wherein especially using diphenylmethyl
Alkane diisocyanate forms polyurethane.The purpose of the document is to avoid during preparing polyurethane water-proof paint using increasing
Mould agent and solvent and toluene di-isocyanate(TDI) (TDI).
CN104877542A discloses a kind of mono-composition poyurethane water-proof paint with high intensity, wherein using isocyanic acid
Ester, amine terminated polyether, end hydroxy polyether form polyurethane prepolymer.
CN102807812A discloses one kind and dives cured mono-composition poyurethane water-proof paint and preparation method thereof.The poly- ammonia
Ester water-repellent paint is grouped as by groups such as diisocyanate, polyether polyol, chlorinated paraffin and latent curing agents.The polyether polyols
Alcohol is the mixture of polyether Glycols and polyether-tribasic alcohol.
However, generally there is also the problems of mechanical performance and weatherability deficiency for water-repellent paint in the prior art.In film
Skinning time and the time being fully cured are very long when solidification, and are also easy to form bubble in surface and film after solidification.This
Outside, the sag resistance of these waterproof membranes and rain proofness and storage stability also remain to be further improved.
Summary of the invention
Therefore, for these deficiencies of the water-repellent paint based on polyurethane of the prior art, the present invention provides one kind such as
The moisture curable of the polyurethane water-proof paint of one pack system described in claim 1, especially one pack system and can liquid apply
Polyurethane water-proof film.
Compared with the prior art, polyurethane water-proof paint of the invention has the improvement at least one following performance, special
It is not to be able to achieve while the improvement or balance on the whole in terms of mechanical performance, weatherability, curability and rain proofness:
For example very high tensile strength of excellent mechanical performance and very high elongation at break and very high tearing strength；
Excellent weatherability, such as 8000h may be implemented there is no crackle；
Good storage stability；
Solidification is rapid, and substantially bubble-free after solidification；
Improved sag resistance and rain proofness；
Moderate viscosity.
Moreover, it relates to by this one pack system polyurethane water-proof paint apply and with contact with moisture after shape
At film, especially waterproof membrane and waterproof system.
Some other preferred embodiment of the invention is the theme of dependent claims.
Detailed description of the invention
The first aspect of the invention is related to a kind of polyurethane water-proof paint of novel one pack system, it includes
- at least one the polyurethane prepolymer formed by polyol component and toluene di-isocyanate(TDI),
- at least one aldimine type latent curing agent,
Wherein the polyol component includes from the trihydroxylic alcohol greater than 50 to 90 weight % and from 10 to less than 50 weight %
Dihydric alcohol, and the average molecular weight of the trihydroxylic alcohol is 3000-6000g/mol and the average molecular weight of the dihydric alcohol is
1000-4000g/mol,
It was found by the inventors of the present invention that if by the latent solid of specific polyurethane prepolymer as described above and aldimine type
Agent combination, it will be able to realize the improvement in those described above performance.In particular, excellent weatherability, improved mechanically performance
And cracking rain proofness.
Herein, term " monocomponent moisture cure " refers to that a kind of liquid applies film, and it includes in single impermeable moisture
In container, there is certain storage life stability and the solidification when being exposed to moisture.
Herein, term " liquid applies (waterproof) film " refers to the material being applied in liquid form as layer on substrate
Material, and its solidification makes substrate waterproof to form elastic membrane.
Herein, term " polyether polyols " includes by all poly- of so-called diisocyanate addition polymerization process preparation
Close object.It includes the polyether polyols of the isocyanate-functional by obtaining polyisocyanates and polyol reaction,
It is properly termed as prepolymer and is polyisocyanates itself.
Particularly, prepolymer is containing at least one, is usually two or more reactive group such as isocyanic acid
The polymer of ester group.Prepolymer can solidify via the reactive group, be crosslinked or chain extension.
Substance title headed by " poly-/more ", such as polyalcohol or polyisocyanates, per molecule on representation herein
Substance comprising two or more functional groups occurred in its title.Such as polyalcohol has at least two or more hydroxyls
Base, and polyisocyanates has two or more isocyanate groups.
Here, it is interpreted as the polyalcohol and two isocyanides for producing polyurethane prepolymer below as starting ingredient
Acid esters and other optional reactants.This more particularly to usage data described below.
Herein, average molecular weight is interpreted as number-average molecular weight, is opposite by gel permeation chromatography (GPC) analysis
It is measured in polystyrene standards.
The method for preparing polyurethane prepolymer of the invention includes optionally in the presence of a catalyst by the polyalcohol group
Divide and is reacted with toluene di-isocyanate(TDI) (TDI) (or mixtures thereof such as 2,4- or 2,6- toluene di-isocyanate(TDI)).Toluene diisocyanate
Acid esters itself is well known to those skilled in the art and can be with the commercially available acquisition of a variety of trades mark.
One or more polyalcohols can be used to prepare polyurethane prepolymer.Although more used in being prepared in polyurethane
First alcohol theoretically can be such as polyether polyol, polyester polyol, polycarbonate polyol, castor oil and its derivative or
The polybutadiene and its mixture of hydroxyl-functional, but the improvement of above-mentioned aspect of performance is realized in scope, it is special
It is not from the aspect of viscosity and water resistance, polyol component is substantially made of polyether polyol, more preferably there is 80 weights
Amount %, preferably 90 weight %, more preferable 95 weight % and particularly preferred 100 weight % are made of polyether polyol.Therefore, accordingly
, above-mentioned trihydroxylic alcohol and dihydric alcohol are preferably respectively one or more polyether triols and one or more polyetherdiol.
It is commercially available for being suitable for the invention these polyether polyol.
What it is particularly suitable as polyether polyol (also referred to as polyoxy sub alkyl polylol) is ethylene oxide, 1,2- epoxy
Or mixtures thereof propane, 1,2- or 2,3- epoxy butane, tetrahydrofuran it is optional by means of have two or more reactive hydrogens
The polymerizate that the starter molecules of atom are polymerize, the starter molecules be, for example, water, ammonia or have multiple OH-
Or the compound of NH- group, such as 1,2- ethylene glycol, 1,2- and 1,3-PD, neopentyl glycol, diethylene glycol, triethylene glycol,
The dipropylene glycol and tripropylene glycol of isomery, the butanediol of isomery, pentanediol, hexylene glycol, heptandiol, ethohexadiol, nonanediol, the last of the ten Heavenly stems two
Alcohol, undecane, 1,3- and 1,4 cyclohexane dimethanol, bisphenol-A, hydrogenated bisphenol A, 1,1,1- trimethylolethane, 1,1,
1- trimethylolpropane, glycerol, aniline and above compound mixture.It can be used for example by means of so-called double gold
Belong to cyanide complex catalyst (DMC- catalyst) preparation have low-unsaturation-degree (according to ASTM D-2849-69 measurement and
Indicated with milliequivalent degree of unsaturation/gram polyalcohol (mEq/g)) polyoxy sub alkyl polylol, also can be used for example by means of
The polyoxy alkylidene with higher degree of unsaturation of anionic catalyst (such as NaOH, KOH or alkali alcoholate) preparation
Polyalcohol.
The polyether polyol is preferably polyoxypropylene glycol, and polyoxypropylene triol, ethylene oxide-capped polyoxy are sub-
Diglycol or ethylene oxide-capped polyoxypropylene triol or its mixture.The polyether polyol is more preferably polycyclic
Oxidative ethane and/or polypropylene oxide.The polyether polyol is most preferably polypropylene oxide.This kind of polyether polyol is commercially available
, such as in trade (brand) nameUnder available commercially from Bayer.So-called ethylene oxide-capped (" EO sealing end ") polyoxy is sub-
Diglycol or triol are equally suitable.They are polyoxypropylene-polyoxyethylene polyalcohols, they for example by with
Under type obtains: polyoxypropylene polyalcohol being carried out alkoxylate with ethylene oxide after propylene oxide polyethylene and is thus had
Primary hydroxyl.
However, it is important in the invention that no matter the type of polyalcohol, the polyol component should comprising compared to
The further amounts of trihydroxylic alcohol of dihydric alcohol, such as comprising from the trihydroxylic alcohol greater than 50 to 90 weight % (such as 60 to 85 weight %) and from 10
To the dihydric alcohol less than 50 weight % (such as 15 to 40 or 45 weight %).It is highly preferred that the polyol component is by the ternary
Pure and mild dihydric alcohol composition.Meanwhile in order to realize above-mentioned beneficial effects of the present invention, it is important that the average mark of trihydroxylic alcohol used
Son amount should be 3000-6000g/mol, such as 3500-5500g/mol, and the average molecular weight of dihydric alcohol is 1000-4000g/
Mol, such as 1200-3500g/mol.
Preferably, the polyurethane prepolymer by 5-30 weight % above-mentioned toluene di-isocyanate(TDI) and 60-95 weight %
Above-mentioned polyol component, optionally in the presence of a catalyst reaction formed.
The polyol component can be for example at 60-160 DEG C with reacting for toluene di-isocyanate(TDI), preferably 80-140 DEG C of model
Temperature in enclosing carries out.Naturally, duration of the reaction depends on temperature used, but may, for example, be 30min-6h, excellent
Select 30min-3h and more preferable 1-1.5h.
In order to carry out the reaction of polyalcohol and toluene di-isocyanate(TDI), conventional metallic catalyst, example can be optionally used
Such as bismuth catalyst, such as from Vertellus Performance MaterialsInc.'s83, Huo Zhexi
Catalyst.
The reaction mixture of the polyurethane prepolymer containing isocyanate-functional is obtained from the reaction.While it is desirable that all
Diisocyanate it is reacted, but the reaction mixture may also comprising a small amount of unconverted diisocyanate, therefore its
Content is, for example, 0-3wt%, such as about 0.5-1wt%, the total weight based on the reaction mixture.It is retained in reaction mixing
HPLC can be used to measure in the content of unconverted diisocyanate in object.
The polyurethane water-proof paint of monocomponent moisture cure according to the present invention further includes at least one aldimine type
Latent curing agent.In the present invention advantageously, the polyurethane water-proof paint of the one pack system only includes the latent solidification of aldimine class
Agent, and do not include other curing agent such as ketimide or oxazolidine.
In a specific embodiment, the latent curing agent is selected from the aldimine of at least one lower formula (I),
Wherein
A is molecular weight in 28 to 5000g/mol range optionally ether-containing or the n valency alkyl portion of carbamate groups
Point,
R1And R2It is identical or different C1To C12The alkyl of linear chain or branched chain, or it is joined together to form the straight chain of divalent
Or the C of branch4To C12Hydrocarbyl portion is a part of 5- to 8- member carbocyclic ring；
R3It is the C of hydrogen or linear chain or branched chain1To C12Alkyl or aralkyl or alkoxy carbonyl,
R4It is monovalence C optionally containing ether, carbonyl or ester group6To C20Hydrocarbyl portion, and
N is 2 to 6.
Preferably, the aldimine type latent curing agent is the aldimine of these following formulas (I):
It is preferred that n is 2 or 3.These aldimines are derived from two or triamine, and film can be made to have good mechanical performance, especially
It is high elongation rate and high-intensitive good combination.
It is preferred that R1And R2It is respectively methyl.These aldimines, which provide, has low viscosity and quick, reliable curing performance
Film.
It is preferred that R3It is hydrogen.These aldimines provide the film with low viscosity and quick, reliable curing performance.
It is preferred that R4It is C11Alkyl.These aldimines provide scentless with low viscosity and high-flexibility at low temperature
Film.
The particularly preferably aldimine of formula (I), wherein R1And R2It is methyl, R3It is hydrogen and R4It is undecyl.These
Aldimine is provided at low temperature with low viscosity, quick and reliable curing performance and high-flexibility scentless film.
Preferably, A be molecular weight 28 to 2000g/mol, particularly 84 to 600g/mol range optionally ether-containing
The n valency alkyl part of base.These aldimines provide have particularly good mechanical performance, flexibility extra high at low temperature and
High intensity under warm conditions.
Preferably, A is remaining part after removing is selected from the primary amino group with the polyamines of the following group: hexa-methylene -1,6- bis-
Amine, 2- methylpentane -1,5- diamines, 3- amino methyl -3,5,5- trimethyl cyclohexylamine (isophorone diamine), 2,2,4- and 2,
4,4- trimethylhexamethylenediamines, 1,3- bis- (amino methyl) benzene, 1,3- bis- (amino methyl) hexamethylenes, the bis- (amino of Isosorbide-5-Nitrae-
Methyl) hexamethylene, bis- (4- aminocyclohexyl) methane, bis- (4- amino -3- methylcyclohexyl) methane, 2,5 (2,6)-bis- (amino
Methyl) bicyclic [2.2.1] heptane, 3 (4), 8 (9)-bis- (aminomethyl)-tricyclic [5.2.1.02,6] decane, 1,2- diamino hexamethylene
Alkane, 1,3- diaminocyclohexane, Isosorbide-5-Nitrae-diaminocyclohexane, 2,2,6- trimethyl-cyclohexanes-Isosorbide-5-Nitrae-diamines, 3,6- dioxas are pungent
Alkane -1,8- diamines, 4,7- dioxadecane -1,10- diamines, 4- aminomethyl-1,2,8- octamethylenediamine, average molecular weight be 200 to
The polyoxypropylene diamine and triamine of 5000g/mol, preferably 200 to 2000g/mol, more preferable 200 to 600g/mol, 1,3-
Phenylenediamine, Isosorbide-5-Nitrae-phenylenediamine, 2,4- and 2,6- toluylene diamines and 4,4 '-, 2,4 '-and 2,2 '-diamino-diphenyl first
Alkane.
In a particularly preferred embodiment of the present, A is when removing the primary amino group of hexa-methylene -1,6- diamines
Remaining part.These aldimines provide the film with special low viscosity and fast curing properties.
In another particularly preferred embodiment of the invention, A is surplus when removing the primary amino group of isophorone diamine
Remaining part.These aldimines, which provide, has especially low viscosity and high-intensitive film.
In another particularly preferred embodiment of the invention, it is 200 to 5000g/ that A, which is when removing average molecular weight,
Mol, preferably 200 to 2000g/mol, the primary amine groups of more preferable 200 to 600g/mol polyoxypropylene diamine or triamine
Remainder.
In very particularly preferred embodiment of the invention, A be when remove average molecular weight 400 to 5000g/mol, preferably
400 to the polyoxypropylene triamine of 500g/mol range primary amino group when remaining part, the triamine especially from
Huntsman'sT-403 perhaps the appropriate level product from BASF or Nitroil or comes from
Huntsman'sT-5000 or appropriate level product from BASF or Nitroil.These aldimines are film
The good combination of very quick curing performance and high elongation rate and intensity is provided.
The aldimine of preferred formula (I) is selected from the group being made up of: N, N '-bis- (2,2- dimethyl -3- laurel acyloxy
Propylidene)-hexa-methylene -1,6- diamines, N, N '-bis- (2,2- dimethyl -3- laurel acyloxy propylidene) -3- amino methyls -
3,5,5- trimethyl cyclohexylamines, bis- (2, the 2- dimethyl -3- laurels of the average molecular weight N 700 to 4600g/mol range, N ' -
Acyloxy propylidene) N, N ', N "-three of-polyoxypropylene diamine and average molecular weight 1200 to 5800g/mol range
(2,2- dimethyl -3- laurel acyloxy propylidene)-polyoxypropylene triamine.
In a particularly preferred embodiment of the invention, the aldimine of formula (I) is N, bis- (2, the 2- dimethyl-of N '-
3- laurel acyloxy propylidene)-hexa-methylene -1,6- diamines.
In another particularly preferred embodiment of the invention, the aldimine of formula (I) is N, bis- (2, the 2- diformazans of N '-
Base -3- laurel acyloxy propylidene) -3- amino methyl -3,5,5- trimethyl cyclohexylamine.
In another particularly preferred embodiment of the invention, the aldimine of formula (I) is N, bis- (2, the 2- diformazans of N '-
Base -3- laurel acyloxy propylidene) (2,2- dimethyl -3- laurel acyloxy is sub- by-polyoxypropylene diamine or N, N ', N "-three
Propyl)-polyoxypropylene triamine.These aldimines, which provide, has especially low viscosity, fast curing properties and high elongation rate
Film.Especially preferably three aldimines.They provide very fast curing performances and high-intensitive good with high elongation rate
Combination.
The aldimine of formula (I) preferably can be anti-from the condensation of the amine of at least one formula (III) and the aldehyde of at least one formula (IV)
It should obtain.
In formula (III) and (IV), A, n, R1、R2、R3And R4With above-mentioned meaning.
For this condensation reaction, the aldehyde of formula (IV) relative to the amine of formula (III) primary amino group with stoichiometry using or with
It is excessively used.The reaction can advantageously 15 to 120 DEG C of ranges at a temperature of carry out, in the presence of the solvent or there is no a solvent
In the presence of carry out.The water discharged is azeotroped off with suitable solvent, or is directly removed in vacuum.
Preferably, content of the aldimine in water-repellent paint is sum and isocyanate groups so that closed amino
Ratio between number is in the range of 0.3 to 1.0 preferably 0.4 to 1.0, more preferable 0.6 to 1.0.Within this range,
The film is rapidly cured as high-intensitive material, without forming bubble or bubble.
In a preferred embodiment of the invention, the polyurethane water-proof paint arrives the above-mentioned of 50wt% comprising 10
Polyurethane prepolymer and 1 to 20wt%, preferably 1 to 10wt% the aldimine type latent curing agent, applied with polyurethane water-proof
Whole component meters of feed composition.Further, in of the invention one preferred embodiment, the polyurethane water-proof
Polyurethane prepolymer component included in coating substantially completely (i.e. more than 95%, preferably greater than 98%, more preferably above
99%, most preferably 100% ground) by above-mentioned at least one polyurethane formed by polyol component and toluene di-isocyanate(TDI)
Prepolymer is constituted.Particularly, the polyurethane prepolymer based on other polyisocyanates is not included in the polyurethane water-proof paint,
Such as based on those of MDI, IPDI or HDI.
Preferably, polyurethane water-proof paint according to the present invention includes at least one filler.Preferred filler is inorganic fills out
Material, especially calcium carbonate (chalk) such as grinding calcium carbonate (GCC) and winnofil (PCC), barium sulfate (barite), slate,
Silicate (quartz), magnesium silicate (talcum) and aluminosilicate (clay, kaolin), dolomite, mica, glass envelope and silicic acid are special
It is not the high dispersive silicic acid (pyrolytic silicon dioxide) from pyrolytic process.These fillers can have or can apply without surface
Layer, such as stearate or silicon coating.
Further preferred filler is organic filler, especially carbon black and microballoon.
Preferably, the water-repellent paint also includes at least one pigment.Preferred pigment is titanium dioxide, iron oxide and charcoal
It is black.
Preferably, the water-repellent paint can also further include the gold of at least one reaction for promoting isocyanate groups
Belong to base catalyst.Preferred metal-based catalyst is dialkyltin complexes, especially stannous methide, dibutyl tin or dioctyl
Tin carboxylate, mercaptides or acetylacetonate, such as DMTDL, DBTDL, DBT (acac)2, DOTDL, neodecanoic acid dioctyl tin
(IV) or DOT (acac)2, bismuth (III) complex compound such as Bismuth Octoate (III) or bismuth neodecanoate (III), zinc (II) complex compound such as octanoic acid
Zinc (II) or zinc neodecanoate (II) and zirconium (IV) complex compound such as zirconium caprylate (IV) or neodecanoic acid zirconium (IV).
The water-repellent paint preferably further includes the acid catalyst of at least one promotion aidimines base hydrolysis.Preferred acid
Catalyst is carboxylic acid and sulfonic acid, especially aromatic carboxylic acid such as benzoic acid or salicylic acid.
The water-repellent paint preferably further includes at least one UV stabilizer.Preferred UV stabilizer is UV absorbent,
Such as benzophenone, benzotriazole, oxanilide (oxalanilides), phenyl triazine and particularly 2- cyano -3,3- diphenyl
Ethyl acrylate and hindered amine light stabilizer (HALS) such as bis- (1,2,2,6,6- pentamethyl -4- piperidyl) sebacates and its
Its compound containing at least one 1,2,2,6,6- pentamethyl -4- piperidinyl moiety.
In addition, the water-repellent paint can further include following component:
Different from other aldimines of the aldimine of formula (I)；
Plasticizer, especially phthalic acid ester, trimellitate, succinate, glutarate, adipate ester, the last of the ten Heavenly stems
Two acid esters, azelate, citrate, benzoic ether, acetylated glycerol or monoglyceride, hydrogenated phthalates, fat
Acid esters, aromatic yl sulphonate or hydrocarbon resins；
Organic solvent such as hydrocarbon, ester or ether, especially pentanedione, Mesityl oxide, cyclohexanone, methyl cyclohexane
Ketone, ethyl acetate, propyl acetate, 1- methoxyl group -2- propyl-acetic acid ester, butyl acetate, diethyl malonate, diisopropyl ether, two
Ether, butyl oxide, ethylene glycol diethyl ether, diethylene glycol diethyl ether, toluene, dimethylbenzene, heptane, octane, diisopropyl naphthalene and stone
Oil distillate such as naphtha, white oil and petroleum ether, such as SolvessoTMSolvent (comes from Exxon), Hydrogenated aromatic solvent such as hydrogenation stone brain
Oil, methylene chloride, propylene carbonate, butyrolactone, N-Methyl pyrrolidone and N- ethyl pyrrolidone；
Additive such as wetting agent, flow enhancing agent, levelling agent, defoaming agent, degasser, desiccant, antioxidant, adherency
Promotor, rheology modifier, especially pyrolytic silicon dioxide and biocide.
When using such other ingredient, it is advantageous that ensure that they will not influence the preservation of uncured film strongly
Phase stability, i.e., the reaction of the crosslinking of polymer during largely triggering does not cause to store.In particular, these other ingredients are not answered
Containing the micro above water.It may be advantageous that physically or chemically drying the ingredient before the use.
Preferably, the water-repellent paint includes:
At least one ingredient selected from inorganic filler and pigment,
At least one ingredient for being selected from catalyst, plasticizer, solvent and UV stabilizer.
The liquid for being preferably based on water-repellent paint of the invention, which applies film, has low viscosity.This makes when as gravity flow
Flat coating has good processability when applying.Particularly, the film is measured with 2000 at 23 DEG C to 15000mPas's
Brookfield viscosity, preferably at 23 DEG C 2000 to 10000mPas range.In the range of viscosities, film is enough to flow automatically
It is flat advantageously to be applied with permission in flat or low gradient roof surface, but do not flow into the small chamber on substrate surface.
The polyurethane water-proof paint of monocomponent moisture cure according to the present invention can by mixed in the case where excluding moisture it is all at
Divide and is prepared with obtaining uniform fluid.It can be stored in the container of suitable impermeable moisture, especially bucket, drum, band
In the cask of snap lid, sack, intestines shape container, cylinder, tank or bottle.
Coating is applied within its open hour with liquid condition, typically via being poured upon on substrate, then will
It spread out, such as with roller or scraper plate, and with the thickness degree needed for obtaining, the thickness is typically in 0.5 to 3mm, especially 0.75
To 1.5mm.
" open hour ", which refer to, herein is exposed to moisture and forms the period between skinning on the surface of the film, also referred to as
" not gluing the time " or " skinning time ".
It is Self-leveling that liquid, which applies film, it means that its viscosity is sufficiently low to establish after being spread by roller or brush
Uniform surface.
When contacting with moisture (moisture in usual atmosphere), the solidification of film starts.Solidification process by chemically react into
Row.Then aidimines base is reacted by moisture-activated with isocyanate groups.When activated, each aidimines base forms primary amino group.This
Outside, isocyanate groups can also directly and reaction of moisture.As these reactions as a result, the film is solidified into solid elastic material
Material.Solidification process is referred to as being crosslinked.After solidification, the elastic material that there is extraordinary adhesiveness to a large amount of substrates is obtained.
The water-repellent paint can be applied on various substrates, and elastic coating is formed on substrate.It can be used in particular for preventing
Water roof, roofdeck or roof garden and flowerpot, balcony, balcony, square or ground.It can also be used to prevent indoors
Water, especially in Ceramic Tiles, such as in bathroom, food and drink kitchen or plant room, protect them from water immersion.It is special that liquid applies film
It is not suitable for overhauling purpose.
It is most preferably used on roof, on especially flat or low gradient roof.It can be used for the anti-of new roof
Water and purpose is overhauled, and particularly useful for niggling.
The liquid that is formed by water-repellent paint of the invention applies a part that film is preferably used as waterproof system, the system by with
Lower composition:
Optionally, priming paint and/or priming coat,
One or more layers described film is preferably combined with fiber reinforcement net or non-woven fibre cloth such as polyester fiber nonwoven cloth,
With
Optionally, top coating.
Liquid apply film preferably pass through following application: be poured upon on substrate, within its open hour by roller, brush,
Diffusion knife or uniformly distributed to the desired thickness degree of scraper, the thickness usually in the range of 0.5 to 3mm, especially exist
In the range of 0.75 to 1.5mm.
Preferably, fiber reinforcement net or non-woven fibre cloth apply after the first layer of the film, by placing it in
Then its roll-in or processing are fully penetrating into film by the top of the film newly applied within the open hour of film, especially by
Roller or brush.Then before optional next tunic applies, the film for mixing fiber reinforcement net is at least cured to it and is suitble to walk
Degree.
It may be advantageous that applying top coating, such as coating varnish to the top layer of film.Especially for based on aromatics isocyanic acid
The film of ester, it is advantageous that anti-ultraviolet top coating is applied on cured film.
Another theme of the invention is the method for making roof structure waterproof, comprising:
It is preferred that with 0.5 to 3mm, particularly 0.75 to 1.5mm range thickness degree by polyurethane water-proof as described above
Coating is applied on the substrate of the roof structure with liquid condition,
Contact the coating with fiber reinforcement net or non-woven fibre cloth,
The coating is exposed to moisture, the coating is either partially or fully cured thus to obtain elastic membrane,
The second tunic is optionally applied with 0.5 to 3mm, particularly 0.75 to 1.5mm range thickness, and passes through exposure
Solidified in moisture.
Fibre reinforced materials net or non-woven fibre cloth are preferably non-woven fibre cloth, such as polyester fiber nonwoven cloth, more preferably
Non-woven fiberglass net.
Fiber reinforcement net or non-woven fibre cloth play the humidification of film, provide increased intensity and durability.Preferred
Non-woven webs in randomly-oriented fiber assign the multidirectional intensity of film, while its being made to keep high flexibility.It is improved
Intensity, tear resistance and puncture resistance.Non-woven glass fibre net, which is shown, to be particularly easy to handle, because it is not rigid,
But it is adapted readily to given surface topography.
The substrate that water-repellent paint of the invention can be applied on it is special are as follows:
Concrete, lightweight concrete, mortar, brick, sun-dried mud brick, watt, slabstone, gypsum and lithotome, such as granite or big
Fibrous gypsum；
Metal and alloy, such as aluminium, copper, iron, steel, non-ferrous metal, metal and alloy including surface finish work are such as zinc-plated
Metal and chrome-plated metal；
Pitch；
Asphalt felt；
Plastics, as PVC, ABS, PC, PA, polyester, PMMA, SAN, epoxy resin, phenolic resin, PUR, POM, PO, PE,
PP, EPM, EPDM, untreated form or are surface-treated with plasma, corona or flame；Especially PVC, PO
(FPO, TPO) or EPDM film；
The substrate of coating, such as japanning ceramic tile, the metal of coating concrete and coating.
Can be the advantageously pretreating substrates before applying film, for example, by washing, pressure wash, wipe, blow off,
Grinding and/or application priming paint and/or priming coat.
By this method, the waterproof roof structure comprising the cured film with incorporation fiber reinforcement net is obtained.
The part on the roof of the preferred building of roof structure, the especially building of structure and civil engineering, preferably house,
Industrial building, hangar, shopping center, movement stadium etc..
Embodiment
It is further described the application by the following examples, but will be clear that the application is not limited to these
Embodiment.
Raw material
The preparation of prepolymer
The preparation of TDI prepolymer:
It is anti-that pre-polymerization synthesis is added in the trihydroxylic alcohol (molecular weight 4800) of 536.1g and 340.8g dihydric alcohol (molecular weight 2000)
It answers in device, oil bath temperature is adjusted to reaction temperature (50 ± 5) DEG C.Under nitrogen protection, urging the TDI of 122.4g and 0.8g
Agent is added rapidly in reaction unit, is warming up to (80 ± 5) DEG C and is carried out prepolymerization reaction.Sampling analysis NCO's contains in reaction process
Amount, when assay value is consistent substantially with design value, reaction was completed, product is encased in sealing container, nitrogen charging hermetic seal.
The preparation of MDI prepolymer:
It is anti-that pre-polymerization synthesis is added in the trihydroxylic alcohol (molecular weight 4800) of 321.7g and 204.5g dihydric alcohol (molecular weight 2000)
It answers in device, oil bath temperature is adjusted to reaction temperature (50 ± 5) DEG C.Under nitrogen protection, urging the MDI of 108.5g and 0.8g
Agent is added rapidly in reaction unit, is warming up to (80 ± 5) DEG C and is carried out prepolymerization reaction.Sampling analysis NCO's contains in reaction process
Amount, when assay value is consistent substantially with design value 5, reaction was completed, product is encased in sealing container, nitrogen charging hermetic seal.
The preparation of prepolymer 1:
It is anti-that pre-polymerization synthesis is added in the trihydroxylic alcohol (molecular weight 4800) of 171.3g and 685.0g dihydric alcohol (molecular weight 2000)
It answers in device, oil bath temperature is adjusted to reaction temperature (50 ± 5) DEG C.Under nitrogen protection, urging the TDI of 143.0g and 0.8g
Agent is added rapidly in reaction unit, is warming up to (80 ± 5) DEG C and is carried out prepolymerization reaction.Sampling analysis NCO's contains in reaction process
Amount, when assay value is consistent substantially with design value, reaction was completed, product is encased in sealing container, nitrogen charging hermetic seal.
The preparation of prepolymer 2:
It is anti-that pre-polymerization synthesis is added in the trihydroxylic alcohol (molecular weight 1000) of 430.4g and 286.9g dihydric alcohol (molecular weight 2000)
It answers in device, oil bath temperature is adjusted to reaction temperature (50 ± 5) DEG C.Under nitrogen protection, urging the TDI of 281.9g and 0.8g
Agent is added rapidly in reaction system, is warming up to (80 ± 5) DEG C and is carried out prepolymerization reaction.Sampling analysis NCO's contains in reaction process
Amount, when assay value is consistent substantially with design value, reaction was completed, product is encased in sealing container, nitrogen charging hermetic seal.
The preparation of prepolymer 3:
Pre-polymerization synthetic reaction is added in the trihydroxylic alcohol (molecular weight 4800) of 476.6g and 317.7g dihydric alcohol (molecular weight 750)
In device, oil bath temperature is adjusted to reaction temperature (50 ± 5) DEG C.Under nitrogen protection, by the catalysis of the TDI of 204.9g and 0.8g
Agent is added rapidly in reaction system, is warming up to (80 ± 5) DEG C and is carried out prepolymerization reaction.The content of sampling analysis NCO in reaction process,
When assay value is consistent substantially with design value, reaction was completed, and product is encased in sealing container, nitrogen charging hermetic seal.
The preparation of prepolymer 4:
It is anti-that pre-polymerization synthesis is added in the trihydroxylic alcohol (molecular weight 4800) of 547.2g and 364.8g dihydric alcohol (molecular weight 6000)
It answers in device, oil bath temperature is adjusted to reaction temperature (50 ± 5) DEG C.Under nitrogen protection, urging the TDI of 87.2g and 0.8g
Agent is added rapidly in reaction system, is warming up to (80 ± 5) DEG C and is carried out prepolymerization reaction.Sampling analysis NCO's contains in reaction process
Amount, when assay value is consistent substantially with design value, reaction was completed, product is encased in sealing container, nitrogen charging hermetic seal.
The preparation of prepolymer 5:
It is anti-that pre-polymerization synthesis is added in the trihydroxylic alcohol (molecular weight 7500) of 537.3g and 358.2g dihydric alcohol (molecular weight 2000)
It answers in device, oil bath temperature is adjusted to reaction temperature (50 ± 5) DEG C.Under nitrogen protection, urging the TDI of 103.7g and 0.8g
Agent is added rapidly in reaction system, is warming up to (80 ± 5) DEG C and is carried out prepolymerization reaction.Sampling analysis NCO's contains in reaction process
Amount, when assay value is consistent substantially with design value, reaction was completed, product is encased in sealing container, nitrogen charging hermetic seal.
The preparation of polyurethane coating
Each polyurethane prepolymer obtained is mixed high-speed stirred with filler, plasticizer and deicer by according to the form below 1, is removed
It is mixed again from different latent solid agent and other additives after water, obtains polyurethane coating composition C1-C4 (root to prepare
According to of the invention) and Ref1-Ref7 (comparative example).
The composition and its dosage of each embodiment coating of table 1
Performance test
Their following performance is measured for each polyurethane coating obtained above as described below and is returned
It receives and is listed in the table below in 2:
Viscosity: it is measured according to ISO 3219
The skinning time: it is measured according to GB-T 16777-2008
Rain proofness: coating composition obtained is formed a film with the coating device of 500 micron thickness, every 10min in film surface
One liang of drop is dripped, and whether observation film surface has recess, and film surface is remained intact the nonpitting duration as when rainwater-proof
Between.
Foaminess: 30-50 grams of coating composition is poured on aluminium sheet, is then immersed in water.It will consolidate after room temperature curing seven days
Film after change is cut from centre, observes film coated surface and section.The visible bubble in bubble that such as detects by an unaided eye is judged as " having bubble ", if
The bubble that detects by an unaided eye is invisible, is judged as " still ".
Weatherability: artificial weathering ageing resistance's test is carried out according to GB-T 23987-2009 method A.According to GB-T
1766-2008 carries out coating aging grading.
Storage stability: being fitted into inflated with nitrogen in closed container for coating composition and seal, and places 7 in 60 DEG C of baking ovens
It.It is taken out after 7 days and places 24 hours and compared according to the measurement viscosity of IS0 3219 and original viscosity, viscosity at room temperature
The more high then storage stability of change rate is poorer, on the contrary then better.
Tensile strength: it is measured according to GB/T 528-2009
Elongation at break: it is measured according to GB/T 528-2009
Tearing strength: it is measured according to GB/T 529-2008
The performance of coating composition summarizes in each embodiment of table 2
* layering is observed in the composition of Ref2.
* observes that storage stability is very poor in the composition of Ref6.
Finally, repeating embodiment C1 to prepare comparative example Ref8, with C1 the difference is that with the latent solidification of ketimide
Agent substitutes aldimine latent curing agent.But the solidification of composition is had occurred and that during the preparation process.
Claims (17)
1. the moisture curable polyurethane water-proof paint of one pack system, includes
- at least one the polyurethane prepolymer formed by polyol component and toluene di-isocyanate(TDI), and
- at least one aldimine type latent curing agent,
Wherein the polyol component includes from the trihydroxylic alcohol greater than 50 to 90 weight % and from 10 to two less than 50 weight %
First alcohol, and the average molecular weight of the trihydroxylic alcohol is 3000-6000g/mol and the average molecular weight of the dihydric alcohol is
1000-4000g/mol。
2. polyurethane water-proof paint according to claim 1, which is characterized in that the average molecular weight of the trihydroxylic alcohol is
3500-5500g/mol, and the average molecular weight of dihydric alcohol is 1200-3500g/mol.
3. according to claim 1 to 2 described in any item polyurethane water-proof paints, which is characterized in that the polyol component packet
Dihydric alcohol containing the trihydroxylic alcohol of weight % from 60 to 85 and 15 to 40 weight %.
4. polyurethane water-proof paint according to any one of claims 1 to 3, which is characterized in that the polyol component has
80 weight %, preferably 90 weight %, more preferable 95 weight % and particularly preferred 100 weight % are made of polyether polyol.
5. polyurethane water-proof paint according to any one of claims 1 to 4, which is characterized in that the trihydroxylic alcohol and binary
Alcohol is respectively one or more polyether triols and one or more polyetherdiol, and the polyether triol and glycol are preferably selected from
Polyoxypropylene glycol, polyoxypropylene triol, ethylene oxide-capped polyoxypropylene glycol or ethylene oxide-capped poly-
Oxygen propylidene triol or its mixture.
6. polyurethane water-proof paint according to any one of claims 1 to 5, which is characterized in that the toluene diisocynate
Ester is or mixtures thereof 2,4- or 2,6- toluene di-isocyanate(TDI).
7. polyurethane water-proof paint according to any one of claims 1 to 6, which is characterized in that the polyurethane prepolymer
By the toluene di-isocyanate(TDI) of 5-30 weight % and the polyol component of 60-95 weight %, optionally in the presence of a catalyst
Reaction is formed.
8. polyurethane water-proof paint according to any one of claims 1 to 7, which is characterized in that the latent curing agent is selected from
The aldimine of at least one lower formula (I),
Wherein
A is molecular weight in 28 to 5000g/mol range optionally ether-containing or the n valency alkyl part of carbamate groups,
R1And R2It is identical or different C1To C12The alkyl of linear chain or branched chain, or it is joined together to form the straight chain or branch of divalent
The C of chain4To C12Hydrocarbyl portion is a part of 5- to 8- member carbocyclic ring；
R3It is the C of hydrogen or linear chain or branched chain1To C12Alkyl or aralkyl or alkoxy carbonyl,
R4It is monovalence C optionally containing ether, carbonyl or ester group6To C20Hydrocarbyl portion, and
N is 2 to 6.
9. polyurethane water-proof paint according to claim 8, wherein the aldimine of the formula (I) is selected from and to be made up of
Group: N, N '-bis- (2,2- dimethyl -3- laurel acyloxy propylidene)-hexa-methylene -1,6- diamines, N, N '-bis- (2,2- diformazans
Base -3- laurel acyloxy propylidene) -3- amino methyl -3,5,5- trimethyl cyclohexylamine, average molecular weight is 700 to 4600g/
Bis- (2,2- dimethyl -3- laurel acyloxy the propylidene)-polyoxypropylene diamines of the N of mol, N '-and average molecular weight exist
1200 to 5800g/mol range N, N ', N "-three (2,2- dimethyl -3- laurel acyloxy propylidene)-polyoxypropylene three
Amine.
10. polyurethane water-proof paint according to any one of claims 1 to 9, further includes
At least one ingredient selected from inorganic filler and pigment, and
At least one ingredient for being selected from catalyst, plasticizer, solvent and UV stabilizer.
11. 1 to 10 described in any item polyurethane water-proof paints are required according to benefit, it includes
- 10 arrive the polyurethane prepolymer of 50wt%, and
- 1 to the 20wt% aldimine type latent curing agent.
12. according to claim 1 to 11 described in any item polyurethane water-proof paints, which is characterized in that the polyurethane water-proof
Whole polyurethane prepolymer included in coating composition has more than 95%, preferably greater than 98%, more preferably above 99%, most
Preferably 100% ground is by least one polyurethane prepolymer structure formed by polyol component and toluene di-isocyanate(TDI)
At.
13. film, by according to claim 1 to 12 described in any item polyurethane water-proof paints apply and with contact with moisture it
After formed, the preferably waterproof membrane on roof.
14. purposes of the film according to claim 13 on roof.
15. waterproof system is made up of:
Optionally priming paint and/or priming coat,
One or more layers film according to claim 13, preferably with fiber reinforcement net or non-woven fibre cloth such as non-woven polyester
Fiber cloth combination, and
Optionally top coating.
16. make the method for roof structure waterproof, including
Roof structure will be applied to liquid condition to 12 described in any item polyurethane water-proof paints according to claim 1
On substrate,
Contact the coating with fiber reinforcement net or non-woven fibre cloth,
The coating is exposed to moisture, so that the coating portion or being fully cured to obtain elastic membrane.
17. waterproof roof structure, method according to claim 16 is obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810353238.0A CN110387187A (en) | 2018-04-19 | 2018-04-19 | The polyurethane water-proof paint of one pack system |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810353238.0A CN110387187A (en) | 2018-04-19 | 2018-04-19 | The polyurethane water-proof paint of one pack system |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111621223A (en) * | 2020-06-22 | 2020-09-04 | 安徽三棵树涂料有限公司 | High-solid-content environment-friendly polyurethane waterproof coating and preparation method thereof |
| CN112159620A (en) * | 2020-09-11 | 2021-01-01 | 临沂斯科瑞聚氨酯材料有限公司 | Waterproof priming coating material for roof concrete |
| CN112323253A (en) * | 2020-10-26 | 2021-02-05 | 浙江王金非织造布有限公司 | Dual-reinforcement non-woven wiping material and preparation method thereof |
| CN113025175A (en) * | 2021-03-16 | 2021-06-25 | 天津中晶建筑材料有限公司 | Moisture-curing polyurethane permeable paint for calcium silicate board and application thereof |
| WO2022111623A1 (en) * | 2020-11-26 | 2022-06-02 | Sika技术股份公司 | Polyurethane composition having reduced foaming and matte effect |
| CN115431187A (en) * | 2022-09-14 | 2022-12-06 | 白鸽磨料磨具有限公司 | Manufacturing method of abrasive cloth with high-flatness sand surface accumulated abrasive |
| CN117567932A (en) * | 2023-12-05 | 2024-02-20 | 科顺防水科技股份有限公司 | Composition for single-component polyurethane waterproof coating, and preparation and application thereof |
| CN117567932B (en) * | 2023-12-05 | 2024-05-14 | 科顺防水科技股份有限公司 | Composition for single-component polyurethane waterproof coating, and preparation and application thereof |
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| WO2012162356A2 (en) * | 2011-05-23 | 2012-11-29 | E. I. Du Pont De Nemours And Company | Anti-corrosion coating composition and use thereof |
| CN104903371A (en) * | 2013-01-22 | 2015-09-09 | Sika技术股份公司 | Liquid-applied waterproofing membrane comprising oxazolidine and aldimine |
| CN106488936A (en) * | 2014-07-09 | 2017-03-08 | Sika技术股份公司 | Waterproof membrane for the liquid application on roof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111621223A (en) * | 2020-06-22 | 2020-09-04 | 安徽三棵树涂料有限公司 | High-solid-content environment-friendly polyurethane waterproof coating and preparation method thereof |
| CN112159620A (en) * | 2020-09-11 | 2021-01-01 | 临沂斯科瑞聚氨酯材料有限公司 | Waterproof priming coating material for roof concrete |
| CN112323253A (en) * | 2020-10-26 | 2021-02-05 | 浙江王金非织造布有限公司 | Dual-reinforcement non-woven wiping material and preparation method thereof |
| WO2022111623A1 (en) * | 2020-11-26 | 2022-06-02 | Sika技术股份公司 | Polyurethane composition having reduced foaming and matte effect |
| CN113025175A (en) * | 2021-03-16 | 2021-06-25 | 天津中晶建筑材料有限公司 | Moisture-curing polyurethane permeable paint for calcium silicate board and application thereof |
| CN115431187A (en) * | 2022-09-14 | 2022-12-06 | 白鸽磨料磨具有限公司 | Manufacturing method of abrasive cloth with high-flatness sand surface accumulated abrasive |
| CN117567932A (en) * | 2023-12-05 | 2024-02-20 | 科顺防水科技股份有限公司 | Composition for single-component polyurethane waterproof coating, and preparation and application thereof |
| CN117567932B (en) * | 2023-12-05 | 2024-05-14 | 科顺防水科技股份有限公司 | Composition for single-component polyurethane waterproof coating, and preparation and application thereof |
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Application publication date: 20191029 |