CN101376685A - Two-solution curing type carbamate composition and construction method of water-proof structure - Google Patents
Two-solution curing type carbamate composition and construction method of water-proof structure Download PDFInfo
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Abstract
The invention provides a method for preparing a two-liquid cured type carbamate composition and waterproof structural body using the same. The composition comprises a main agent (I) and curing agent (II). The main agent comprises carbamate prepolymer (A) having at least three isocyanate groups at terminal and prepared from polyisocyanate and polyoxyalkylene polyol by reacting, and a carbamate compound (B) having oxazo-lidinyl at the terminal. The curing agent comprises a retarder (C) comprising at least one organic acid metal salt and water in oil type emulsion (D). The organic acid metal salt can be organic acid potassium, organic acid Cobalt, organic acid copper, organic acid iron, organic acid calcium, organic acid zinc, organic acid aluminum, organic acid zirconium, organic acid barium, organic acid lithium, organic acid nickel, organic acid neodymium and organic acid tin. The water content of the water in oil type emulsion (D) is 0.1-1.5wt% of the two-liquid cured type carbamate composition containing the compounds (A), (B), (C) and (D).
Description
Technical field
The present invention relates to a kind of two-solution curing type carbamate composition with good package stability, with constructional method used as the water-proof structure of water-proof material, wherein said composition still can keep serviceable time, the coating operation at initial stage after prolonged preservation, and from constant to solidifying the needed time after the end of job.
Background technology
As the moisture-curable carbamate composition of water-proof material in the past, the moisture-curable coating water-proof material that known technology relates to be made up of the moisture-curable prepolymer, wherein the polyvalent alcohol is made up of the polyvalent alcohol that makes the oxirane addition polyethers that contains specified quantitative or ethylene oxide unit of this moisture-curable carbamate and organic diisocyanate react and obtain (for example with reference to patent documentation 1).But therefore this technology exists the frequent expansible problem of filming because said composition produces carbonic acid gas when moisture and isocyanic ester radical reaction when solidifying.
Therefore, generation for the carbonic acid gas that suppresses to become the expansion reason, proposed the linking agent of moisture dissociative types such as ketoimine, enamine, the composition of wherein known Han oxazolidine (for example with reference to patent documentation 2 and patent documentation 3) does not produce carbonic acid gas, is that performance is than the isostatic material.
But because the curing reaction that causes because of moisture from film coated surface slowly, therefore, when impasto, the shortcoming of said composition is that to solidify the needed time significantly elongated.
Therefore, the solidified nature when improving thick being coated with, the applicant has proposed a kind of carbamate composition, has added in the said composition to make water and as the lead octoate 36 (with reference to patent documentation 4) of urethane catalyzer.
But the problem that this carbamate composition exists is if use after prolonged preservation, then can not fully obtain to compare with the serviceable time at initial stage the coating activity duration that shortens.
Patent documentation 1: TOHKEMY is opened flat 1-38825 communique
Patent documentation 2: Japanese kokai publication hei 6-293821 communique
Patent documentation 3: Japanese kokai publication hei 7-10949 communique
Patent documentation 4: TOHKEMY 2006-219655
Summary of the invention
Problem of the present invention provides a kind of preparation method who has the carbamate composition of good package stability and use its civil construction thing water-proof structure, wherein said composition is after prolonged preservation finishes, can keep serviceable time at initial stage, coating operation, and from constant to solidifying the needed time after the end of job.
Inventors of the present invention have carried out research with keen determination to above-mentioned problem, it found that: if in use, the water of the retardant that will form by specific metal salts of organic acids and the specified quantitative of specific modality, sneak in the carbamate compounds of carbamate prepolymer and terminal Han oxazolidine base, then find to have the composition of good package stability, said composition is after prolonged preservation finishes, can keep serviceable time at initial stage, coating operation, and from constant to solidifying the needed time after the end of job.
Promptly, the invention provides the constructional method of a kind of two-solution curing type carbamate composition and the water-proof structure that uses it, it is characterized in that: said composition comprises host (I) and solidifying agent (II), host (I) comprises the end that is obtained by polyisocyanates and polyoxyalkylene polyol reaction and has the polyurethane prepolymer (A) of 2 above isocyanate group and the carbamate compounds (B) of terminal Ju oxazolidine base, solidifying agent (II) comprises retardant (C) and the W/O be made up of at least a metal salts of organic acids and drips type emulsion (D), this metal salts of organic acids is an organic acid potassium, the organic acid cobalt, organic acid manganese, copper organic acid, organic acid iron, calcium of organic acid, organic acid zinc, organic acid aluminium, the organic acid zirconium, organic acid barium, the organic acid lithium, organic acid nickel, organic acid neodymium and organic acid tin, and the water content that aforementioned W/O drips type emulsion (D) is 0.1～1.5wt% in carbamate composition.
Even two-solution curing type carbamate composition of the present invention still can keep serviceable time at initial stage, coating operation after prolonged preservation, and to finish the needed time constant up to solidifying after the end of job, also has good storing stability.In addition, in the constructional method of water-proof structure, even these materials of prolonged preservation also can be guaranteed certain activity duration, and since shorter after the end of job up to the needed time of curing, so can shorten the activity duration significantly.
Embodiment
Below the present invention is illustrated in further detail.
The host (I) that the present invention uses comprises the end that is obtained by organic multiple isocyanate and polyoxyalkylene polymers reaction to be had the carbamate prepolymer (A) of two above isocyanate group and is generating the carbamate compounds (B) of Ju oxazolidine base on the end of primary amino or secondary amino group with the water reaction.
The carbamate prepolymer (A) that above-mentioned end has two above isocyanate group is to use well-established law, under the condition of organic multiple isocyanate base surplus aforementioned organic multiple isocyanate and polyoxyalkylene polyol is reacted modulation and obtains.
As this polyisocyanates, can exemplify 2, the 4-tolylene diisocyanate, 2, the 6-tolylene diisocyanate, '-diphenylmethane diisocyanate, make the '-diphenylmethane diisocyanate of a part of carbonization imideization, polymethylene polyphenyl Quito isocyanic ester, tolylene diisocyanate, naphthalene diisocyanate, phenylene vulcabond, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, the hydrogenation xylylene diisocyanate, hydrogenated diphenyl methane diisocyanate, aromatic diisocyanates such as cyclohexyl diisocyanate, aliphatic diisocyanate, alicyclic diisocyanates etc. can use the mixture more than a kind or 2 kinds of these materials.
Composition component polyoxyalkylene polyol as aforementioned carbamate prepolymer (A) can be by add one or more polyvalent alcohols that make such as polyoxyethylene, propylene oxide, oxybutylene on ethylene glycol, propylene glycol, water, glycerine, TriMethylolPropane(TMP), tetramethylolmethane etc.
It is 500～16000 that the molecular weight of aforementioned polyoxyalkylene polyol is preferably number-average molecular weight.
As polyoxyalkylene polyol,, preferably add the polyvalent alcohol of polyoxyethylene from improving coating after fixing aspect.
In the case, comprise in the composition of host (I) of carbamate prepolymer (A) and aftermentioned carbamate compounds (B), the content of ethylene oxide chain is less than 10wt% in host (I) is formed preferably from the water tolerance aspect.
The mean number of the isocyanate group that carbamate prepolymer (A) is terminal is preferably more than 2 preferred especially 3.
Particularly in the reaction of polyvalent alcohol and polyisocyanates, the isocyanate group in the preferred polyisocyanates is more than 1.4 with respect to the mol ratio (NCO/OH mol ratio) of hydroxyl groups, wherein more preferably 1.4～4.0.
The amount of residual isocyanate group is preferably 1～20wt% in the carbamate prepolymer (A).
Though carbamate prepolymer (b1) and N-2 Qiang Wan Ji oxazolidine (b2) reaction that the carbamate compounds (B) of the employed terminal Ju oxazolidine base of host of the present invention (I) makes the end that is obtained by polyisocyanates and polyoxyalkylene polyol reaction have 2 above isocyanate group obtain, it is good especially aspect solidified nature and thermotolerance.
Such carbamate prepolymer (b1) can use and the identical material of aforementioned carbamate prepolymer (A), also can use and the different material of carbamate prepolymer (A).
From the solidified nature aspect, the polyoxyalkylene polyol that is used for carbamate prepolymer (b1) preferably has the ethylene oxide chain as oxyalkylene chain.In the case, the content of preferred especially ethylene oxide is 1～30wt% of oxidative chain.If the content of ethylene oxide chain is in this scope, then it has higher curing speed, good solidified nature and water tolerance.
By aforementioned record, if comprise the content of the ethylene oxide chain in the host (I) of carbamate compounds (B) of carbamate prepolymer (A) and terminal Ju oxazolidine base and be 10wt% when above, water tolerance may reduce, so as the ethylene oxide chain of polyvalent alcohol during less than 10wt%, the polyvalent alcohol that preferably will not contain the oxyethylene chain is sneaked in the polyvalent alcohol that contains the oxyethylene chain and is used.
The number-average molecular weight of carbamate prepolymer (b1) is preferably 500～8000.If number-average molecular weight, then can satisfy good ground tracing ability in this scope, curing speed shortens.
In addition, the average isocyanate number of ester groups of the end of carbamate prepolymer (b1) is preferably 2.0～2.6.If this isocyanic ester radix in this scope, then solidified nature and ground tracing ability excellence.More properly, the ratio of polymeric polyisocyanate and polyvalent alcohol adopts the mol ratio (NCO/OH mol ratio) of isocyanate group/hydroxyl to be preferably more than 1.6, is preferably 1.8～4.0 especially.The content of residual isocyanate group is preferably 1～15wt% in the carbamate prepolymer.
The ratio of aforementioned carbamate prepolymer (b1) and N-2-Qiang Wan Ji oxazolidine (b2), the preferred isocyanate base is 0.95～3.0 with the mol ratio (NCO/OH) that contains N-2-Qiang Wan Ji oxazolidine (b2) hydroxyl.If NCO/OH is this scope, then the tendency owing to remaining unreacted N-2-Qiang Wan Ji oxazolidine diminishes, so the spendable time is elongated, and can suppress the reduction of curing speed and the rising of viscosity.
Aforementioned N-2-Qiang Wan Ji oxazolidine (b2) can make by the known condensation reaction of aldehydes such as for example formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, phenyl aldehyde and for example dihydroxyalkyl such as diethanolamine, dipropanolamine amine.Oxazolidinyl can adopt water to carry out open loop, generates amino and hydroxyl.
The end end oxazolidine radix of described carbamate compounds (B) is preferably average 1～3.In this scope, then the stretchiness of cured article improves as fruit oxazolidine radix.
Also can there be isocyanate group in the end of carbamate compounds (B) except that Cun Zai oxazolidinyl.
The blending ratio that is used for carbamate prepolymer of the present invention (A) and aforementioned carbamate compounds (B), the mol ratio of the isocyanate group of preferred carbamate prepolymer (A) and the carbamate compounds (B) of the aforementioned terminal Ju oxazolidine base active hydrogen atom that open loop produces in water are 0.4～4.0 scope.If be this scope, then the generation of carbonic acid gas is few, the expansion that can suppress to film.
If consider this aspect, the ratio of mixture (weight ratio) of carbamate prepolymer (A) and aforementioned carbamate compounds (B) is preferably 60: 1～1: 30 scope in the host (I).
On the one hand, constitute solidifying agent of the present invention (II) and comprise by being selected from retardant (C) that following at least a metal salts of organic acids forms and being that the aqueous W/O of 0.1～1.5wt% drips type emulsion (D) with respect to two-solution curing type carbamate composition of the present invention, wherein this metal salts of organic acids is organic acid potassium, organic acid cobalt, organic acid manganese, copper organic acid, organic acid iron, calcium of organic acid, organic acid zinc, organic acid aluminium, organic acid zirconium, organic acid barium, organic acid lithium, organic acid bismuth, organic acid nickel, organic acid neodymium and organic acid tin.
The retardant of being made up of the aforementioned metal salts of organic acids of solidifying agent of the present invention (II) use (C) is preferably the aliphatic acid metal-salt, and it for example can be exemplified as: potassium octanoate, cyclic potassium naphthenate, neodecanoic acid potassium, calcium octoate, calcium naphthenate, neodecanoic acid calcium, cobalt octoate, cobalt naphthenate, new cobalt decanoate, iron octoate, iron naphthenate, neodecanoic acid iron, manganese octoate, manganese naphthenate, neodecanoic acid manganese, zirconium caprylate, zirconium naphthenate, cupric oleate, stannous octoate, aluminium octoate, tallow fatty acid barium, ricinolic acid barium, neodecanoic acid barium, alkyl (C=12～20) terephthalic acid lithium, the dibutyl nickel dithiocarbamate, the neodecanoic acid neodymium.Its addition is preferably 0.001～0.4wt% based on carbamate composition as amount of metal, particularly 0.05～0.02wt%.
Even in the retardant of being made up of these metal salts of organic acids (C), from after long storage, set out in the effect aspect of the good storing stability that the serviceable time is constant, and preferred especially is the calcium of organic acid of representative by calcium octoate, calcium naphthenate, neodecanoic acid calcium.
Content from the calcium of calcium of organic acid is preferably 0.001～0.4wt% with respect to two-solution curing type carbamate composition of the present invention, the more special 0.005～0.02wt% that is preferably.If calcium contents is in the scope of 0.001～0.4wt%, then the prolongation effect of serviceable time is abundant, also can overslaugh not solidify.If in the scope of 0.001～0.4wt%, then can infer aforementioned metal salts of organic acids and can produce with certain of water and combine, can suitably delay water and the aforementioned carbamate compounds (ring-opening reaction of B) De oxazolidinyl that W/O drips type emulsion (D) as retardant.In addition, drip type emulsion (D) if will sneak into the aftermentioned W/O by the retardant of forming (C) of metal salts of organic acids, to constitute aforementioned (A) of host (I) and (B) component, with aforementioned (C) that constitute solidifying agent (II) and (D) component mixing, then owing to form two-solution curing type, so its transaction capabilities is good, thus preferred.Because aforementioned retardant (C) is easy to mix with aforementioned (A), (B), (D) component, so be preferably the solution that is dissolved in aftermentioned solvent and/or softening agent.
The W/O that solidifying agent of the present invention (II) uses drip type emulsion (D) as external phase as under the oil condition, W/O drips type emulsion (hereinafter referred to as w/o type emulsion) as emulsion, because itself and external phase are that oil droplet type emulsion (O/W type emulsion) is different in the water under the situation of water, so be also referred to as w/o type emulsion.By aforementioned (A) of amino formate and (B) Combination and the serviceable time of the host (I) formed of component can prolong, so must be w/o type emulsion.Though the carbamate prepolymer (A) of host (I) and (B) component be easy to react owing to containing isocyanate group with water, adopt W/O to drip type emulsion (D), can obtain the effect that Combination and serviceable time prolong.W/o type emulsion is scattered in the aqueous hydrophobic compound (d1) as the particle that contains water (d2) at normal temperatures.
Liquid hydrophobic compound (d1) under the aforementioned normal temperature can be the aqueous oily compound under the normal temperature, can use for example softening agent such as Viscotrol C, rapeseed oil and derivative thereof (specifically being the reaction product of castor-oil plant wet goods and glycerine etc.), polyoxyalkylene polyol, 2-phthalic acid (ethyl hexyl) ester, especially preferably use the reaction product of Viscotrol C or Viscotrol C and glycerine, this is because it can improve the Combination of the host (I) of hydrophobicity and raising and carbamate prepolymer composition.
Water-content in the present composition is 0.1～1.5wt% with respect to the total amount of being mixed the carbamate composition that forms by host (I) and solidifying agent (II), wherein preferred especially 0.2～0.8wt%.If the amount of water is 0.1～1.5wt%, then when thick being coated with, the film coated surface and inner difference set time of filming are less, and the activity duration is also elongated.
Such water is not independent water, is the shape that W/O drips type emulsion (D), adopts the inside of hydrophobic compound film to be made up of water particle in the outside, and (C) mixes with the retardant of being made up of specific metal salts of organic acids, may carry out prolonged preservation.
Aforementioned W/O drip type emulsion (D) by with aforementioned hydrophobic compound (d1) and aforementioned water (d2) is disposable or will be wherein one part add gradually, be 10～50 ℃ for example in temperature, adopt dispersion machine etc. to stir at a high speed and be prepared from.The ratio of mixture of aforementioned hydrophobic compound (d1) and aforementioned water (d2) is preferably the scope of 60～90:10～40 (weight ratio).
When the aforementioned W/O of preparation drips type emulsion (D), if desired,, preferably use emulsifying agent (d3) for water (d2) stable dispersion is arrived in the aforementioned hydrophobic compound (d1).
Aforementioned emulsifying agent (d3) can use known emulsifying agent.What wherein preferably have good emulsifying stability is known polyoxyalkylene polyols such as polyoxyethylene lauryl ether, polyoxyethylene three decyl ethers, polyoxyethylenated castor oil ether.
Consider aforementioned W/O drip type emulsion (D) with the host of forming by carbamate (I) when mixing; because the water in the emulsion is subjected to the protection of hydrophobic group; so slowly be diffused in the two-solution curing type carbamate composition of the present invention, therefore can obtain long serviceable time and activity duration.
Aforementioned emulsion (D) can adopt known method that emulsifying agent (d3) and water (d2) are evenly spread in the hydrophobic compound (d1) and be prepared, and in water and oil, dissolved emulsifier (d3) can form external phase preferably.
Aforementioned emulsion (D) with contain carbamate prepolymer (A) and have the host (I) of carbamate of oxazolidine base endways when mixing, owing to, can before closing on use, be mixed in the carbamate composition with described carbamate compounds (B) reaction.
In the host (I) or solidifying agent (II) of the amino formate water-proof material that uses two-solution curing type carbamate composition of the present invention, if necessary, can contain Zuo Wei oxazolidinyl dissociation catalyst acid, organic solvent, inorganic filler, process oil, softening agent, thixotropic agent, pigment extender, be used to keep various additives such as the ultraviolet screener that improves weathering resistance, stablizer etc.For these additives are carried out uniform mixing, and guarantee its keeping quality, can adopt kneading device to carry out thorough mixing and prepare.
As mix, kneading device, can be exemplified as the butterfly mixing tank of hermetic type and planetary-type mixer etc.
Though can adopt for example known acid such as Whitfield's ointment, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, mellitic acid and its acid anhydrides as the acid of dissociation catalyst, wherein preferred especially terephthalic acid, Whitfield's ointment.
Can use carbamate solvent commonly used such as toluene, dimethylbenzene, turps, acetic acid ethyl ester as solvent.
As thixotropic agent, for example can give an example surface treatment lime carbonate, polyvinyl chloride powder, micropowder silicon-dioxide, wilkinite etc.In addition, can also be that high boiling point fragrance family cut, petroleum resin etc. are sneaked into carboxylamine ester mixture of the present invention with oil.
As softening agent, for example can exemplify esters such as dibutyl phthalate, dioctyl phthalate (DOP), the two undecyl esters of phthalic acid, dilauryl phthalate, butyl benzyl phthalate, Di Iso Decyl Phthalate, Polycizer W 260, Octyl adipate, diisononyl adipate, dioctyl azelate, dioctyl sebacate is that softening agent or phosphoric acid ester such as trioctyl phosphate, triphenylphosphate are softening agent.
As stablizer, for example can exemplify oxidation inhibitor, UV light absorber etc.As inorganic filler, for example can exemplify the powder body of mineral compound such as lime carbonate, calcium oxide, clay, talcum, titanium oxide, Tai-Ace S 150, kaolin, diatomite, glass sphere.In composition, its addition is preferably 5～70wt%, more preferably 10～60wt%.
Carbamate composition of the present invention can be used as water-proof material, when being used to apply water-proof structure, uses same material or differing materials can repeat coating, particularly can be used as top layer and is applied to the surface.
The ratio of mixture of host of the present invention (I) and solidifying agent (II) is preferably 100:0.1～100:10 (weight ratio).Host (I) and solidifying agent (II) can adopt cutter, rod etc. to mix, and also can adopt the mixing machine of agitator etc. to mix, and after mixing, preferably are coated with as quickly as possible.
As the constructional method of water-proof structure, after primer coating, the water-proof material that coating is made up of carbamate composition of the present invention.
The constructional method of the present composition that uses as water-proof material can adopt modes such as blade coating, trowelling, extruding to be coated with.In addition, also can adopt spraying machine to spray.The coating number of times of water-proof material is generally 1～2 time, and each glue spread is preferably 0.5～5kg/m
2, 1.0～4.0kg/m more preferably
2
Do the roof, balcony of the apartment can be exemplified as the buildings formed by concrete, timber, pitch, iron, aluminium etc. etc., tame family dwelling house etc. etc. as the civil construction owner of coating.
Priming paint when using as coating can be exemplified as the priming paint of the carbamate water-proof material of moisture-curable carbamate resins, two-solution curing type Resins, epoxy, water system acrylic resin, water system propenyl carbamate resins etc. for example as known priming paint.
Priming paint adopts roller, bristle, spatula etc. that substrate is generally about 0.02～0.04kg/m with glue spread
2Ratio coating once.In the case, if necessary, the coating number of times that can be coated with is 1～4 time.In addition, if necessary, can after in advance with mixing such as tackiness agent and sand, be coated with.
When being coated with water-proof material thereon, must be with the priming paint drying.
After primer coating, be generally 2～96 hours up to the desirable time of ensuing engineering.Surpassing under 96 hours the situation, preferably primer coating once more.
The constructional method of water-proof structure of the present invention is the waterproof method in the roof that is used for the balcony of door dwelling house and buildings, parking lot etc.
Embodiment
Below, the present invention is described in detail with comparative example in conjunction with the embodiments, but the present invention is not limited to these embodiment.In the following, " part " reaches " % " if there is not special instruction, is weight basis.
Reference example 1: the preparation example of carbamate prepolymer (A-1)
In the polypropylene ether triol 300g (0.1 mole) of the butene propylene ether glycol 700g (0.35 mole) of number-average molecular weight 2000, number-average molecular weight 3000, add 2 with 50% butylene ehter bond, 4-tolylene diisocyanate 191.4g (1.1 moles), the equivalence ratio that is NCO/OH is 2.2, under nitrogen gas stream, 80 ℃, in flask, make its reaction 18 hours while stirring, obtain isocyanate group (NCO%) and be 4.25% carbamate prepolymer.Below this carbamate prepolymer is called carbamate prepolymer A-1.
Reference example 2: the preparation example of carbamate prepolymer (A-2)
In reference example 1, the oxygen ethylene content that uses number-average molecular weight 2000 except the butene propylene ether glycol 700g (0.35 mole) that replaces number-average molecular weight 2000 is 10% the polyethylene propylene ether glycol 700g (0.35 mole), adopt with the same method of reference example 1 syntheticly, obtain NCO% and be 4.26% carbamate prepolymer.Below this carbamate prepolymer is called carbamate prepolymer A-2.
The preparation example of reference example 3: An base Jia Suan Zhi oxazolidine prepolymer (OXZ-1)
With the amount of number-average molecular weight 4800, ethylene oxide chain is that 15% the polyethylene propylene ether triol 500g (0.104 mole) and the polypropylene ether glycol 500g (0.25 mole) of number-average molecular weight 2000 mix, and the average amount that obtains the ethylene oxide chain is 7.5%, average sense radix is 2.29, number-average molecular weight is 2820 polyvalent alcohol.And then adding hexamethylene diisocyanate 143.3g (0.853 mole), the equivalence ratio that is NCO/OH is 2.1, under nitrogen gas stream, 80 ℃, in flask, make its reaction 48 hours while stirring, obtain NCO% and be 3.28%, the terminal NCO radix of per 1 molecule is 2.29 carbamate prepolymer.
With carbamate prepolymer 140.8g and the 2-sec.-propyl-3-(2-hydroxyethyl)-1 that obtains, 3-oxazolidine 15.9g, (equivalence ratio of NCO/OH is 1.1), under nitrogen gas stream, 60 ℃, in flask, make its reaction 48 hours while stirring, obtain An base Jia Suan Zhi oxazolidine prepolymer (hereinafter referred to as OXZ-1).
The results verification that the GPC of above-mentioned OXZ-1 is measured: unreacted remaining 2-sec.-propyl-3-(2-hydroxyethyl)-1, the containing ratio of 3-oxazolidine is below 1%.
Reference example 4: the preparation example of carbamate prepolymer composition (host (I))
With 410 parts of NS-500 (lime carbonate, day eastern efflorescence system), wherein, moisture is adjusted to below 0.05% 95 parts of dioctyl phthalate (DOP)s with its drying under reduced pressure 5 hours in 120 ℃ of hermetic type planetary-type mixers, 0.15 part Whitfield's ointment, 5 parts of Powdered terephthalic acids, 290 parts of carbamate prepolymer A-1 are after 210 parts of OXZ-1 and 80 parts of dimethylbenzene carry out uniform mixing, under the decompression of 50 holders, carry out deaeration, make carbamate prepolymer composition (host (I)) M-1.
Reference example 5: the preparation example of carbamate prepolymer composition (host (I))
Adopt 290 parts of 290 parts of carbamate prepolymer A-1 in the carbamate prepolymer A-2 replacement M-1 prescription, adopt identical method to make carbamate prepolymer composition (host (I)) M-2 then.
Reference example 6: the preparation example of carbamate prepolymer composition (M-3)
Except in the prescription of M-1, not adding the aforesaid OXZ-1, adopt identical blending means to make carbamate prepolymer composition M-3.
Reference example 6: W/O drips the preparation example of type emulsion (E-1)
Adopt agitator, with 67 parts of ユ-リ Star Network-H (Viscotrol C, she rattan essential oil system), the 3 parts of ニ ユ-コ as emulsifying agent-Le 1103 (polyoxyethylene lauryl, Japanese emulsifying agent system, ProductName) and 3 parts of water carry out uniform mixing, make w/o type emulsion.This emulsion is called E-1.
Reference example 7: W/O drips the preparation example of type emulsion (E-2)
SYNTEGRA YM-2000 (water-content is a droplet-shaped emulsion in 43% the urethane resin system, ダ ウ ケ ミ カ ル System) is called E-2.
Embodiment 1～7 and comparative example 1～7
Under table-1, table-2 and table-3 mixing conditions of being put down in writing, each host (I) and solidifying agent (II) component are mixed the preparation carbamate composition.Carry out following test.Test-results is shown in table-1, table-2 and table-3.
Test method
Solidified nature test-initial cure the time
Adopt 100g/m
2Ratio, with プ ラ イ ア デ Star Network T-41 (amino formate prepolymer, big Japanese ink chemical industry system) is applied to sticking the slabstone of release paper around the frame encirclement (on 30 * 30cm), after at room temperature (17～18 ℃ * 45～50% RH) leaves standstill 2 hours, with the ratio coating water-proof material of 3mm thickness, place then at room temperature (15～20 ℃ * 40～60%).Mensuration is designated as the initial cure time up to filming the motionless time with the finger contact with it.The first operation time
The time of repose (2 hours) of priming paint is counted the activity duration with the total ascent time of the set time of water-proof material.
The mensuration of serviceable time at initial stage
Host (I) and the solidifying agent (II) of adjusting to 25 ℃ were in advance mixed 1 minute with the blending ratio of defined, then container is put in the sampling of 100g mixture,, adopt BM type rotational viscosimeter to assign to measure viscosity with 6rpm/ at 25 ℃.To begin to reach time till 100,000 mPas as serviceable time (branch) from mixing to viscosity.
The stable storing type
Solidifying agent (II) mixture was preserved 6 months at 23 ℃, after after preservation, stirring, adopted the measuring method of aforesaid serviceable time at initial stage, initial cure time to measure serviceable time and set time.
The coating operation
Coating 2mm is thick on the slabstone of 90 * 90cm, mixes the solidifying agent (II) and the host (I) of preserving 6 months, estimates the operation that is coated with when adopting spatula coating method coating operation.
O: good *: bad (coating operational difficulty)
Table 1
*5% neodecanoic acid calcium: calcium contents is 5% plasticizer solution.
Table 2
*: 5% neodecanoic acid calcium: calcium contents is the plasticizer solution of 5wt%
*: 24% lead octoate 36: lead content is the solvent solution of 24wt%
Table 3
Comparative example 7
Existing two-solution curing type carbamate, adopt and do not use the host of forming by the carbamate prepolymer of isocyanate group end (the デ イ Star Network carbamate N big Japanese ink chemical industry of host (strain) system), with by ammonia, many alcohols solidifying agent (デ イ Star Network carbamate N solidifying agent, big Japanese ink chemical industry (strain) system) carbamate composition of Zu Cheng De oxazolidinyl carbamate compounds, its set time, activity duration, serviceable time are shown in reference to using table 4.
Table 4
Annotate 1): デ イ Star Network carbamate N host (carbamate prepolymer of NCO end, big Japanese ink chemical industry (strain) system)
Annotate 2): デ イ Star Network carbamate N solidifying agent (ammonia, many alcohols, big Japanese ink chemical industry (strain) system)
Embodiment 1 and 2 demonstrates the good curing performance with suitable serviceable time.
Embodiment 3 is owing to used the W/O of carbamate resins to drip type (W/O) emulsion, so compare with embodiment 2, the serviceable time is tended to shorten, and set time is good.
Embodiment 4 has certain growth set time owing to the water content that W/O drips type emulsion is 0.15wt% with respect to carbamate composition, so compare with 4 with comparative example 3, demonstrates excellent results.
Embodiment 5, compares with comparative example 1 so the serviceable time is tended to shorten owing to the water content that W/O drips type emulsion is 1.2wt% with respect to carbamate composition, and the serviceable time is elongated, and set time is also good.
Embodiment 6, compares with comparative example 1 so the serviceable time is tended to shorten owing to the calcium metal content from metal salts of organic acids is 0.0025wt% with respect to carbamate composition, and the serviceable time is long, and set time is good.
Content from the calcium metal of metal salts of organic acids among the embodiment 7 is 0.02wt% with respect to carbamate composition, so that the serviceable time is tended to is elongated, compares with 3 with comparative example 2, and set time is good.
Use W/O to drip in the solidifying agent (II) of type emulsion (D), metal salts of organic acids and retardant composition, make the comparative example 1 of water separately, its serviceable time is very short, is the level that cannot use.
Do not use the comparative example 2 of solidifying agent (II) component because airborne moisture makes it be cured from the surface, so the result be solidify very slow.
Only use the comparative example 3 of the retardant of forming by the metal salts of organic acids of solidifying agent (II) (C), consequently solidify very slow.
Adopt 24% lead octoate 36 to replace the comparative example 4 of the retardant (C) is made up of metal salts of organic acids, consequently after solidifying agent (II) was preserved, its serviceable time significantly shortened, and practicality is lower.
Use comparative example 5 and the comparative example 6 of host (I) M-3 that does not add OXZ-1, when solidifying, produce foaming, can not form uniform coating as water-proof material owing to producing carbon dioxide gas.In addition, owing to do not add OXZ-1, use the retardant of forming by metal salts of organic acids (C) just can not find the effect of its serviceable time delay (OXZ-1 dissociate the retarding effect of speed).
In addition, use the comparative example 7 of existing two liquid water-proof materials, do not relate to embodiment and compare the substantially the same serviceable time, its set time of filming is longer, and the result is that its activity duration is also longer.
Claims (8)
1. two-solution curing type carbamate composition, it is characterized in that: said composition comprises host (I) and solidifying agent (II), host (I) comprises the end that is obtained by polyisocyanates and polyoxyalkylene polyol reaction and has the carbamate prepolymer (A) of 2 above isocyanate group and the carbamate compounds (B) of terminal Ju oxazolidine base, solidifying agent (II) comprises retardant (C) and the W/O be made up of at least a metal salts of organic acids and drips type emulsion (D), this metal salts of organic acids is selected from organic acid potassium, the organic acid cobalt, organic acid manganese, copper organic acid, organic acid iron, calcium of organic acid, organic acid zinc, organic acid aluminium, the organic acid zirconium, organic acid barium, the organic acid lithium, organic acid nickel, organic acid neodymium and organic acid tin, and the water content of aforementioned (D) is containing aforementioned (A), (B), (C) and be 0.1～1.5wt% in the two-solution curing type carbamate composition (D).
2. according to the two-solution curing type carbamate composition of claim 1 record, the carbamate compounds (B) of wherein aforementioned terminal tool oxazolidine base obtains for carbamate prepolymer (b1) and N-2-hydroxyl alkane base oxazolidine (b2) reaction that the end that is obtained by polyisocyanates and polyoxyalkylene polyol reaction has two above isocyanate group.
3. according to the two-solution curing type carbamate composition of claim 1 or 2 records, wherein aforementioned retardant (C) is a calcium of organic acid.
4. according to the two-solution curing type carbamate composition of claim 3 record, wherein from the calcium contents in aforementioned retardant (C) calcium of organic acid in containing aforementioned (A), (B), (C) and two-solution curing type carbamate composition (D), be 0.001～0.4wt%.
5. according to the two-solution curing type carbamate composition of claim 1 or 2 records, the water-content that wherein aforementioned W/O drips type emulsion (D) is 0.1～0.8wt% in aforementioned two-solution curing type carbamate composition.
6. according to the two-solution curing type carbamate composition of claim 1 or 2 records, wherein aforementioned W/O drips type emulsion (D) and obtains for adopting emulsifying agent (d3) that water (d2) is dispersed in the hydrophobic compound (d1).
7. according to the two-solution curing type carbamate composition of any record in claim 1 and 2, the hydrophobic compound (d1) that wherein aforementioned W/O drips type emulsion (D) is the Viscotrol C or derivatives thereof.
8. the constructional method of a water-proof structure is characterized in that adopting claim 1 or 2 two-solution curing type carbamate compositions of putting down in writing.
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| CN104640894A (en) * | 2012-09-11 | 2015-05-20 | Sika技术股份公司 | Two-component polyurethane composition |
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| JP4013163B2 (en) * | 2005-01-11 | 2007-11-28 | 大日本インキ化学工業株式会社 | Urethane composition |
| JP4720259B2 (en) * | 2005-04-05 | 2011-07-13 | 横浜ゴム株式会社 | Two-component curable polyurethane resin composition |
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