CN1330716C - Wet gas solidifying type carbamate composition - Google Patents
Wet gas solidifying type carbamate composition Download PDFInfo
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- CN1330716C CN1330716C CNB2004100049476A CN200410004947A CN1330716C CN 1330716 C CN1330716 C CN 1330716C CN B2004100049476 A CNB2004100049476 A CN B2004100049476A CN 200410004947 A CN200410004947 A CN 200410004947A CN 1330716 C CN1330716 C CN 1330716C
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- carbamate
- terephthalic acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60S—SERVICING, CLEANING, REPAIRING, SUPPORTING, LIFTING, OR MANOEUVRING OF VEHICLES, NOT OTHERWISE PROVIDED FOR
- B60S1/00—Cleaning of vehicles
- B60S1/02—Cleaning windscreens, windows or optical devices
- B60S1/04—Wipers or the like, e.g. scrapers
- B60S1/32—Wipers or the like, e.g. scrapers characterised by constructional features of wiper blade arms or blades
- B60S1/40—Connections between blades and arms
- B60S1/4006—Connections between blades and arms for arms provided with a hook-shaped end
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60S—SERVICING, CLEANING, REPAIRING, SUPPORTING, LIFTING, OR MANOEUVRING OF VEHICLES, NOT OTHERWISE PROVIDED FOR
- B60S1/00—Cleaning of vehicles
- B60S1/02—Cleaning windscreens, windows or optical devices
- B60S1/04—Wipers or the like, e.g. scrapers
- B60S1/32—Wipers or the like, e.g. scrapers characterised by constructional features of wiper blade arms or blades
- B60S1/40—Connections between blades and arms
- B60S1/4067—Connections between blades and arms for arms provided with a side pin
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The moisture curable urethane composition comprises: (A) a urethane prepolymer which contains a polyoxyalkylene ring in molecule and has at least two terminal isocyanate groups; (B) a urethane compound which has at least one terminal oxazolidine group and is obtained by reacting a urethane prepolymer (b1) containing a polyoxyalkylene ring in molecule and having at least two terminal isocyanate groups and/or polyisocyanate (b2) and an N-2-hydroxyalkyl oxazolidine (b3); and (C) a terephthalic acid micropowder whose 90 wt% or more has a diameter of 106 micrometers or less.
Description
Technical field
Filming when the present invention relates to solidify does not have foaming, and solidified nature, excellent heat resistance are even and impregnated in and film in the buck that also not have outward appearance unusual, the moisture-curable carbamate composition that the rerum natura conservation rate is high.
Background technology
As moisture-curable carbamate composition in the past, the known prepolymer that is obtained by the reaction of the polyvalent alcohol that makes the ethylene oxide unit that contains specified quantitative and organic diisocyanate (for example constitutes, open clear 57-94056 communique with reference to the spy), but, there is the problem that paint blister often takes place because said composition produces carbonic acid gas when moisture and isocyanic ester radical reaction when solidifying.
In the past for the generation of the carbonic acid gas that suppresses to become the expansion reason, the linking agent of moisture dissociative types such as ketoimine, enamine, azoles alkane has been proposed, the carbamate composition that wherein uses azoles alkane (for example, with reference to the spy open flat 6-293821 communique, the spy opens flat 7-33852 communique and the spy opens flat 7-10949 communique) do not produce carbonic acid gas, be that performance is than the isostatic material.
But these carbamate compositions have the tendency of poor heat resistance, have therefore proposed by containing the moisture-curable carbamate composition (for example, the spy opens flat 11-322894 communique) that terephthalic acid makes the thermotolerance improvement.But the cured article that is generated by the commercially available carbamate composition that contains terephthalic acid if impregnated in the buck etc., has and produces space, degraded appearance in filming, or the tendency that reduces of the conservation rate of rerum natura.
Summary of the invention
The invention provides films when solidifying does not have foaming, and solidified nature, excellent heat resistance are even and impregnated in and film in the buck that also not have outward appearance unusual, the moisture-curable carbamate composition that the rerum natura conservation rate is high.
Inventors of the present invention have carried out research with keen determination to this problem, it found that: because commercially available terephthalic acid particle diameter is big, it is unusual to produce appearance of film when impregnated in buck, unusual in order to improve this outward appearance, if using the crystallization particle diameter that contains specified quantitative is the terephthalic acid of the following particle of 106 μ m, then do not exist the appearance of film that produces by buck unusual, the conservation rate height of rerum natura.Thereby finished the present invention based on these experiences.
That is, the invention provides the moisture-curable carbamate composition, it contains: contain the carbamate prepolymer (A) that polyoxyalkylene chain, end have at least 2 isocyanate group in the molecule; Make and contain in the molecule that polyoxyalkylene chain, end have the carbamate prepolymer (b1) of at least 2 isocyanate group and/or polymeric polyisocyanate (b2) and N-2-hydroxyalkyl azoles alkane (b3) reaction and the end that obtains has the carbamate compounds (B) of at least 1 oxazolidinyl; Reach and have the terephthalic acid particulate (C) of the following particle diameter of 106 μ m more than the 90 weight %.
Embodiment of the present invention
Below the present invention is described in more detail.
Containing carbamate prepolymer (A) [hereinafter referred to as carbamate prepolymer (A)] that polyoxyalkylene chain, end have 2 above isocyanate group in the molecule used in the present invention makes polymeric polyisocyanate and polyoxyalkylene polyol reaction and obtains.
As this polymeric polyisocyanate, can exemplify 2, the 4-tolylene diisocyanate, 2, the 6-tolylene diisocyanate, '-diphenylmethane diisocyanate, make the '-diphenylmethane diisocyanate of a part of carbodiimideization, polymethylene polyphenyl base polymeric polyisocyanate, tolylene diisocyanate, naphthalene diisocyanate, phenylene diisocyanate, 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.But, be not limited to these examples.
In addition, as aforementioned polyoxyalkylene polyol, for example can exemplify polyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol etc.These polyoxyalkylene polyols can make by independent or two or more interpolation oxyethane, propylene oxide, oxybutylene etc. in ethylene glycol, propylene glycol, water, glycerine, TriMethylolPropane(TMP), tetramethylolmethane etc. with currently known methods.But be not limited to these examples.Be conceived to operation, solidified nature is good, preferably the number-average molecular weight of this polyoxyalkylene polyol is 500～16000.
Carbamate prepolymer used in the present invention (A) reaches with respect to hydroxyl under the superfluous ratio aforementioned polymeric polyisocyanate and aforementioned polyoxyalkylene polyol modulated with well-established law, in the isocyanate group of representing with equivalence ratio and obtains.Specifically, the mol ratio of preferred isocyanate base and polymeric polyisocyanate and hydroxyl groups (NCO/OH ratio) is more than 1.4, wherein is preferably 1.4～5.0 especially.Be conceived to operation, solidified nature is good, the amount of isocyanate group is 1～20 weight % in the carbamate prepolymer (A).
Aforementioned carbamate prepolymer (A) from the water tolerance aspect, preferably contains the polyoxybutylene chain as polyoxyalkylene chain, and the balanced aspect from solidified nature etc. preferably contains the polyoxytrimethylene chain.And then, can contain polyethylene oxide chain in case of necessity.
Carbamate prepolymer (A) preferably contains the polyoxybutylene chain of 5～80 weight %, preferably contains the polyoxytrimethylene chain of 20～95 weight %.The polyethylene oxide chain that can contain 0～10 weight %.
It is good to be conceived to solidified nature, and the terminal isocyanate group number of carbamate prepolymer (A) is preferably more than 2, is preferably 2～3 especially.
In addition, the end used in the present invention carbamate compounds (B) [hereinafter referred to as azoles alkylamino formic acid ester compound (B)] that has 1 oxazolidinyl at least make have polyoxyalkylene chain in the molecule, carbamate prepolymer (b1) that end has 2 above isocyanate group or polymeric polyisocyanate (b2) and N-2-hydroxyalkyl azoles alkane (b3) reaction obtain.
Can use aforementioned carbamate prepolymer (A) as having the carbamate prepolymer (b1) [hereinafter referred to as carbamate prepolymer (b1)] that polyoxyalkylene chain, end have 2 above isocyanate group in the molecule, but, preferably use carbamate prepolymer (A) carbamate prepolymer in addition from the solidified nature aspect.
From the curing speed aspect, solidified nature and water tolerance aspect, preferably the polyoxyalkylene chain of this carbamate prepolymer (b1) contains polyethylene oxide chain.This polyethylene oxide chain that contains 1～30 weight % in the preferred polyoxyalkylene chain.Other constituents of polyoxyalkylene chain are polyoxytrimethylene chain, polyoxybutylene chain.
With respect to the total amount of aforementioned carbamate prepolymer (A) and carbamate prepolymer (b1), polyethylene oxide chain is preferably less than 10 weight % in aforementioned carbamate prepolymer (A) and the carbamate prepolymer (b1).If be this scope, then have excellent in water resistance.
The number-average molecular weight of carbamate prepolymer (b1) is preferably 500～8000.If number-average molecular weight in this scope, then can satisfy ground tracing ability, curing speed.
The average isocyanate number of ester groups of the end of carbamate prepolymer (b1) is preferably 2.0～2.6.If be this isocyanic ester radix, then solidified nature and ground tracing ability excellence.In addition, the ratio of isocyanic ester and polyvalent alcohol preferably is adjusted into NCO/OH and reaches more than 1.6, is preferably 1.8～4.0 especially.The content of isocyanate group is preferably 1～15 weight % in the carbamate prepolymer (b1).
In addition, be used to make the N-2-hydroxyalkyl azoles alkane (b3) of azoles alkylamino formic acid ester compound (B), can make by aldehydes such as for example formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, phenyl aldehyde and for example condensation reaction of dihydroxyalkyl such as diethanolamine, dipropanolamine amine.But be not limited to these examples.
The number of the terminal oxazolidinyl of azoles alkylamino formic acid ester compound (B) is preferably 1～3.If be this scope, the stretchiness after the curing improves, and can obtain good rerum natura.Can have at least 1 oxazolidinyl at the end of carbamate oxazolidine compound (B), other ends can be other functional groups beyond the oxazolidinyl.
Carbamate prepolymer (b1) and N-2-hydroxyalkyl azoles alkane (b3), the mol ratio of preferred isocyanate base and hydroxyl (NCO/OH) is 0.95～3.0.If NCO/OH is this scope, the tendency of then remaining unreacted N-2-hydroxyalkyl azoles alkane diminishes, and storage stability improves, and is easy to suppress the reduction of curing speed and the rising of viscosity.
As polymeric polyisocyanate used in the present invention (b1), can use polymeric polyisocyanate as the raw material record of aforementioned carbamate prepolymer (A).
The ratio of carbamate prepolymer (A) and azoles alkylamino formic acid ester compound (B), the equivalence ratio (NCO/H) that the isocyanate group of preferred carbamate prepolymer (A) and azoles alkylamino formic acid ester compound (B) active hydrogen atom that open loop produces in water contains base reaches 0.4～4.0 scope, more preferably reaches 0.5～2.5 scope.If be this scope, the generation of carbonic acid gas is few, the expansion that can suppress to film, storage stability excellence.If consider this aspect, carbamate prepolymer (A) and the azoles alkylamino formic acid ester compound (B) represented with weight ratio are preferably (A): (B)=and 60: 1～1: 30 scope.
The terephthalic acid particulate (C) that has the following particle diameter of 106 μ m among the present invention more than the employed 90 weight % means that 90 weight % of terephthalic acid are above and is made of the terephthaldehyde's acid particles with the following particle diameter of 106 μ m.Be preferably the terephthalic acid particulate that has the following particle diameter of 106 μ m more than the 95 weight %.In addition, its median size is preferably 1～60 μ m.In addition, terephthalic acid particulate of the present invention is preferably the terephthalic acid of purity more than 98%.
The commercially available product of terephthalic acid, with the result of dry screen point-score test: median size is 70～120 μ m, and in addition, the content of terephthaldehyde's acid particles that particle diameter 106 μ m are following is 70～85 weight %.When the terephthaldehyde's acid particles below the particle diameter 106 μ m only contains less than 90 weight %, cured coating film be impregnated in the buck, produce the space with the alkali cpd reaction, become and cause bad order, or the reason of rerum natura reduction.
The particle diameter of terephthalic acid particulate used in the present invention (C) is represented to measure and the numerical value that obtains by dry screen point-score or Microtrac FRA (MOUNTECH Co., Ltd. makes).
So-called dry screen point-score is meant the different various screen clothes of particle diameter that use regulation among the JIS-Z-8801-1 (2000), carries out the method for particle screening with dry type.So-called particle diameter is the following particles of 106 μ m, is meant that having passed through the nominal perforate is the particle of the screen cloth of 106 μ m.MicrotracFRA (MOUNTECH Co., Ltd. makes) is for measuring the device of mashed prod particle diameter.
Terephthalic acid particulate used in the present invention preferably with mixing machine with aforesaid commercially available product terephthalic acid and aqueous polyoxyalkylene polyol, after for example the polypropylene glycol of number-average molecular weight 1000～5000, polytetramethylene glycol, polyoxyethylene glycol etc. and dewatering agent (tetraethyl orthosilicate etc.) mix, carry out fragmentation dispersion and make with dispersion machine.The commercially available terephthalic acid and the blending ratio of polyoxyalkylene polyol are represented with weight ratio, preferred 1: 0.8～1.2, and more preferably 1: 1.
The mixing machine of this moment can exemplify dish-shaped mixing machine, kneader etc., as dispersion machine, can exemplify tumbling mill, ball mill, ball mill etc.
In addition, after can brokenly disperseing, remove the polyoxyalkylene polyol that uses during broken dispersion the etc., or when with the amount of 40～60 quality % when residual, even under the situation of not removing, also can be used as it is.If be the polyoxyalkylene polyol of this polyvalent alcohol amount, then be mixed into easily in the constituent, therefore improved blending dispersion.So because terephthalic acid particulate (C) homogeneous disperses, the alkali resistance of filming improves, be difficult for producing the space.
If using more than the 90 weight % that obtain like this is the terephthalic acid particulate of the following particle diameter of 106 μ m, even a small amount of the interpolation, thermotolerance also obviously improves, and also not produce appearance of film in the buck unusual even cured coating film be impregnated in, and can bring into play the high excellent effect of rerum natura conservation rate.
Preferred 0.05～20 weight % of the amount of this terephthalic acid particulate (C).If less than 0.05%, then thermotolerance raising effect is little, cooperates if surpass 20 weight %, can't expect the effect that thermotolerance further improves.More preferably 0.1～10 weight %, further preferred 0.1～5 weight %.
Moisture-curable carbamate composition of the present invention, preferably further containing the naphthalene of number-average molecular weight more than 150 is hydrocarbon and/or the alkane hydrocarbon system hydrocarbon of number-average molecular weight more than 150.
As the naphthalene of number-average molecular weight more than 150 is hydrocarbon and the alkane hydrocarbon system hydrocarbon of number-average molecular weight more than 150, for example can exemplify tridecane, the tetradecane, pentadecane, n-Hexadecane, cyclododecane, ring tridecane, the ring tetradecane etc.In addition, as commercially available product, can exemplify エ Network ソ one Le D-80 (number-average molecular weight 177: エ Network ソ Application chemistry is made), エ Network ソ one Le D-110 (number-average molecular weight 217: エ Network ソ Application chemistry is made), エ Network ソ one Le D-130 (number-average molecular weight 240: エ Network ソ Application chemistry is made) etc.But be not limited to these examples.If use the hydrocarbon of above-mentioned number-average molecular weight more than 150, then volatility reduces, and the shrinkability of cured article also reduces.
The naphthalene of number-average molecular weight more than 150 is that the amount of hydrocarbon and/or the alkane hydrocarbon system hydrocarbon of number-average molecular weight more than 150 is preferably 1～15 weight %.If be the scope of 1～15 weight %, be suitable viscosity then, operation is good, and the coating characteristic of cured article is also excellent.
In addition, from the environmental safety aspect, wish that moisture-curable carbamate composition of the present invention does not contain organic solvent.
Moisture-curable carbamate composition of the present invention in case of necessity can further contain catalyzer, inorganic filler, softening agent, thixotropic agent, pigment extender, be used to keep various additives such as the ultraviolet screener of raising weathering resistance, stablizer etc.
As this additive,, wish not contain organic solvents such as toluene definite in the organic solvent rule of the Japanese law of labour safety and health, dimethylbenzene from the environmental safety aspect.
Moisture-curable carbamate composition of the present invention can by the above-mentioned raw materials homogeneous is mixed, the mixing manufacturing.
As being used for mixing kneading device this moment, can exemplify planetary-type mixer etc.
As thixotropic agent, for example can exemplify surface treatment lime carbonate, polyvinyl chloride powder, micropowder silicon-dioxide, wilkinite etc.In addition, can also and be high boiling point fragrance family cut, petroleum resin etc. with oil.
As catalyzer, can use known Whitfield's ointment or dibutyl tin laurate catalyzer such as (DBTDL).
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 moisture-curable carbamate composition of the present invention, its addition is preferably 5～70 weight %, more preferably 10～60 weight %.
As purposes, moisture-curable carbamate composition of the present invention can be used for coating material, sealing material, tackiness agent etc.
As coating material, can be used for roof flashing material, parking lot water-proof material, wall material, the flooring material of coating, buildings, the surperficial pavement material in stadium etc.
In addition, as sealing material, can be used for buildings such as concrete, filler plate, metal with sealing material for building.
In addition, as tackiness agent, can be used for the tackiness agent of tackiness agent, the ceramic tile of tackiness agent, the roof water-proof plate of buildings built-in materials such as plastic floor material, the tackiness agent of sheet material, natural stone, pottery, rubber, wooden even-granular thing, fibrous material.
In these purposes, from excellent heat resistance, impregnated in and not produce the unusual aspect of the outward appearance of filming in the buck and set out, particularly use concrete as the purposes of ground in effectively.
Embodiment
Below, the present invention will be described in detail to reach 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.
Synthesizing of synthesis example 1[carbamate prepolymer (A)]
In the polypropylene ether triol 300g (0.1 mole) of the polybutene ether glycol 700g (0.35 mole) of number-average molecular weight 2000, number-average molecular weight 3000, add 2,4-tolylene diisocyanate 191.4g (1.1 moles), promptly the equivalence ratio at NCO/OH is 2.2, under nitrogen gas stream, 80 ℃, in flask, make its reaction 15 hours while stirring, obtain isocyanate group and be 4.25% carbamate prepolymer.Below this carbamate prepolymer is called carbamate prepolymer (A-1).
Synthesizing of synthesis example 2[carbamate prepolymer (A)]
In synthesis example 1, use the polypropylene ether glycol 700g (0.35 mole) of number-average molecular weight 2000 except the polybutene ether glycol 700g (0.35 mole) that replaces number-average molecular weight 2000, adopt and use the same method syntheticly, obtain isocyanate group and be 4.28% carbamate prepolymer.Below this carbamate prepolymer is called carbamate prepolymer (A-2).
Synthesizing of synthesis example 3[ azoles alkylamino formic acid ester compound (B)]
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), promptly the equivalence ratio at NCO/OH is 2.1, under nitrogen gas stream, 80 ℃, in flask, make its reaction 48 hours while stirring, obtain isocyanate group and be 3.28%, the terminal NCO radix of per 1 molecule is 2.29 carbamate prepolymer.Below this carbamate prepolymer is called carbamate prepolymer (b1-1).
With carbamate prepolymer (b1-1) 140.8g and 2-sec.-propyl-3-(2-hydroxyethyl)-1,3- azoles alkane 15.9g, equivalence ratio at NCO/OH is 1.1, under nitrogen gas stream, 60 ℃, in flask, make while stirring its reaction 48 hours, obtain carbamate oxazolidine compound (hereinafter referred to as OXZ-1).
The results verification that the GPC of above-mentioned OXZ-1 is measured: remaining 2-sec.-propyl-3-(2-hydroxyethyl)-1, the containing ratio of 3- azoles alkane is below 1%.
Modulate the modulation of routine 1[terephthalic acid particulate/polyoxyalkylene polyol mixture]
Be pre-mixed 15 minutes with dish-shaped mixing machine with terephthalic acid 500g and polypropylene ether glycol 500g and as the tetraethyl orthosilicate 20g of dewatering agent at normal temperatures, use 3 roller mixing rolls then mixing 3 times, carry out fragmentation and disperse, obtain the mixture of terephthalic acid particulate 50 weight % and polypropylene ether glycol 50 weight %.
With the size-grade distribution of terephthalic acid particulate in Microtrac FRA (MOUNTECH Co., Ltd. makes) the mensuration mixture, results verification: having 98 weight % particle diameters is the following particles of 106 μ m, and median size is 40 μ m.
Embodiment 1～3 and comparative example 1～4
The aforementioned carbamate prepolymer that obtains, OXZ-1, terephthalic acid are cooperated in the cooperation ratio of table-1 and table-2, then in the hermetic type planetary-type mixer, 120 ℃ of following drying under reduced pressure 5 hours, interpolation is adjusted to 380 parts in lime carbonate below the 500ppm (day eastern efflorescence system NS-200), 90 parts of 2-ethylhexyl phthalic esters, 0.1 part of Whitfield's ointment with moisture, after homogeneous mixes, under the decompression of 60 holders, carry out deaeration, obtain the moisture-curable carbamate composition.
Secondly, for the aforementioned moisture-curable carbamate composition that obtains, carry out viscosity, solidified nature, non-foaminess, shrinking percentage, stretching rerum natura, thermotolerance and alkali-proof test.
[test method and metewand]
Viscosity: test portion is adjusted to 25 ℃, use BM type rotary viscosity design determining viscosity.
Solidified nature: around surrounding and the sheet glass that sticks release paper (on 30 * 30cm), flows test portion with the ratio of thickness 1.5mm, places under the condition of 25 ℃ * humidity 50%, measure up to filming the motionless time with finger touch with frame.
Non-foaminess: (on 30 * 30cm), with the ratio of thickness 2mm test portion is flowed, after it was solidified, the visual observation film coated surface had or not foaming, pin hole to the slabstone around surrounding with frame.
Metewand be do not have to bubble, pin hole is designated as zero, have foaming, pin hole be designated as *.
Shrinking percentage: the slabstone around surrounding with frame (on 30 * 30cm), with the ratio of thickness 2mm test portion is flowed, in that maintenance is after 7 days under 23 ℃ the condition, film by formation.This is filmed cut into the short palisade of 2.5 * 30cm.After correctly having measured lateral length, maintenance is after 7 days in 50 ℃ drying machine, and the horizontal length of correct once more mensuration with the length comparison before 50 ℃ of maintenances, is asked for by the shrinking percentage that calculating is filmed.
Stretching rerum natura: around surrounding and stick the sheet glass of release paper (on 30 * 30cm), with the ratio of thickness 1.5mm test portion is flowed, after placing 14 angels under the condition of 23 ℃ * humidity 50% it solidifies, formation is filmed with frame.Use tensile testing machine, under the condition of draw speed 500mm/min, measure the tensile strength (N/cm of this normality of filming
2) and extension at break (%).
Thermotolerance: according to normality stretching rerum natura test method(s), make test portion, taking-up after 80 ℃ under this test portion being maintained 7 days in drying machine.Then after placing 24 hours under the condition of 23 ℃ * humidity 50%, according to normality stretching rerum natura test method determination tensile strength (N/cm
2) and extension at break (%).
Alkali resistance: according to normality stretching rerum natura test method(s), make test portion, this test portion flood taking-up after 5 days in 23 ℃ cement water saturation solution, visual outward appearance is observed.Then, after placing 24 hours under the condition of 23 ℃ * humidity 50%, according to normality stretching rerum natura test method determination tensile strength (N/cm
2) and extension at break (%).
In addition,, in test portion, do not produce be designated as " nothing " in space, produce be designated as " the space generation " in space for appearance change
The matching requirements of moisture-curable carbamate composition and test-results are shown in table-1, table-2 and table-3.
Table-1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |||
| Cooperate | Carbamate prepolymer A-1 | ?290 | ?- | ?290 | |
| Carbamate prepolymer A-2 | ?- | ?290 | ?- | ||
| OXZ-1 | ?210 | ?210 | ?210 | ||
| Ultra-micro powder TPA | ?2 | ?5 | ?2 | ||
| D-80 | ?80 | ?80 | ?- | ||
| ソルベッソ200 | ?- | ?- | ?80 | ||
| Viscosity (mPa/25 ℃) | ?5700 | ?5900 | ?5200 | ||
| Solidified nature (hrs) | ?6 | ?7 | ?7 | ||
| Non-foaminess | ?○ | ?○ | ?○ | ||
| Shrinking percentage (%) | ?-0.8 | ?-0.9 | ?-2.1 | ||
| Normality | Tensile strength | ?3.3 | ?3.1 | ?2.9 | |
| Extension at break | ?550 | ?590 | ?505 | ||
| After heat-resisting | Tensile strength | ?3.1 | ?3.1 | ?2.7 | |
| Extension at break | ?580 | ?550 | ?525 | ||
| After alkaline-resisting | Appearance change | Do not have | Do not have | Do not have | |
| Tensile strength | ?3.1 | ?2.4 | ?2.8 | ||
| Extension at break | ?580 | ?680 | ?550 | ||
Table-2
| Comparative example 1 | Comparative example 2 | Comparative example 3 | |||
| Cooperate | Carbamate prepolymer A-1 | ?290 | ?290 | ?290 | |
| OXZ-1 | ?210 | ?210 | ?210 | ||
| Commercially available TPA | ?2 | ?5 | ?- | ||
| Micropowder TPA | ?- | ?- | ?2 | ||
| D-80 | ?80 | ?80 | ?80 | ||
| Viscosity (mPa/25 ℃) | ?5300 | ?5200 | ?5500 | ||
| Solidified nature (hrs) | ?9 | ?8 | ?9 | ||
| Non-foaminess | ?○ | ?○ | ?○ | ||
| Shrinking percentage (%) | ?-0.9 | ?-1.0 | ?-1.0 | ||
| Normality | Tensile strength | ?2.7 | ?2.7 | ?3.0 | |
| Extension at break | ?570 | ?540 | ?575 | ||
| After heat-resisting | Tensile strength | ?2.0 | ?2.5 | ?2.5 | |
| Extension at break | ?700 | ?590 | ?710 | ||
| After alkaline-resisting | Appearance change | The space produces | The space produces | The space produces | |
| Tensile strength | ?1.2 | ?1.0 | ?1.8 | ||
| Extension at break | ?415 | ?380 | ?425 | ||
Table-3
| Comparative example 4 | Comparative example 5 | |||
| Cooperate | Carbamate prepolymer A-1 | ?290 | ?500 | |
| OXZ-1 | ?210 | ?- | ||
| Commercially available TPA | ?- | ?2 | ||
| Micropowder TPA | ?- | ?- | ||
| D-80 | ?80 | ?80 | ||
| Viscosity (mPa/25 ℃) | ?5800 | ?5500 | ||
| Solidified nature (hrs) | ?9 | More than 24 | ||
| Non-foaminess | ?○ | ?× | ||
| Shrinking percentage (%) | ?-0.8 | ?-1.3 | ||
| Normality | Tensile strength | ?2.8 | ?2.1 | |
| Extension at break | ?580 | ?805 | ||
| After heat-resisting | Tensile strength | ?1.2 | ?1.8 | |
| Extension at break | ?815 | ?935 | ||
| After alkaline-resisting | Appearance change | Do not have | Do not have | |
| Tensile strength | ?2.4 | ?1.8 | ||
| Extension at break | ?575 | ?950 | ||
In table-1, table-2 and the table-3, ultra-micro powder TPA, commercially available TPA, micropowder TPA, D-80, ソ Le ベ ッ ソ 200, heat-resisting back and the following meaning of alkaline-resisting back expression.
Ultra-micro powder TPA: the terephthalic acid particulate that obtains in the modulation example 1.The terephthalic acid amount of the following particle diameter of 106 μ m is that 98 weight %, median size are the terephthalic acid of 40 μ m.
Commercially available TPA: the terephthalic acid that Mitsubishi Chemical makes, the terephthalic acid amount of the following particle diameter of 106 μ m is that 75 weight %, median size are the terephthalic acid of 90 μ m.
The terephthalic acid amount of the following particle diameter of micropowder TPA:106 μ m is that 86 weight %, median size are the terephthalic acid of 57 μ m.
D-80: the naphthalene of number-average molecular weight 177 is that hydrocarbon and isoparaffin are the mixture (エ Network ソ Application chemistry is made) of hydrocarbon.
ソ Le ベ ッ ソ 200: the fragrant family hydrocarbon of number-average molecular weight 1 66 (エ Network ソ Application chemistry is made).
Heat-resisting back: in aforesaid thermal test method, with the rerum natura after the test portion heating.
Alkaline-resisting back: in aforesaid alkaline resistance test method, test portion be impregnated in rerum natura behind the cement water saturation solution.
Shown in table-1, table-2 and table-3, consequently: the material excellence of embodiment, when the constituent of comparative example 1 that has used the commercially available product terephthalic acid and comparative example 2 impregnated in the buck, the rerum natura conservation rate was low, produced space, appearance poor in filming.In addition, the terephthalic acid amount that has used the following particle diameters of 106 μ m is the comparative example 3 of the micropowder terephthalic acid of 86 weight % when impregnated in the water, and filming also produces the space, appearance poor, impregnated in buck after rerum natura also remarkable low than normality.Though without the no bad order in comparative example 4 bucks of terephthalic acid dipping back, significantly reduction and be not suitable for practicality of thermotolerance.In addition, do not contain the comparative example of oxazolidine compound, curing is slow and foaminess is poor, is not suitable for practicality.
The effect of invention
Wet gas solidifying type carbamate composition of the present invention, owing to film when solidifying without foaming, curing property, excellent heat resistance, therefore can be widely used as coating material, encapsulant, adhesive etc., film in the buck also without abnormal appearance even particularly impregnated in, the conservation rate of physical property is high, is that concrete purposes is very useful for ground therefore.
Claims (5)
1, moisture-curable carbamate composition, it contains:
Contain the carbamate prepolymer (A) that polyoxyalkylene chain, end have at least 2 isocyanate group in the molecule, wherein carbamate prepolymer (A) be polymeric polyisocyanate and polyoxyalkylene polyol in the isocyanate group that makes polymeric polyisocyanate is that NCO/OH reacts under than=1.4～5.0 condition and obtains with respect to the mol ratio of hydroxyl groups;
Make and contain polyoxyalkylene chain, end in the molecule and have the carbamate compounds (B) that the carbamate prepolymer (b1) of at least 2 isocyanate group and/or end that polymeric polyisocyanate (b2) obtains with N-2-hydroxyalkyl azoles alkane (b3) reaction have at least 1 oxazolidinyl; And
Terephthalic acid particulate (C), when being total amount 100 weight % with terephthalic acid particulate (C), terephthalic acid particulate (C) contains and has passed through below the above 100 weight % of terephthalic acid particulate 90 weight % of screen cloth that the nominal perforate is 106 μ m;
Wherein, the ratio of carbamate prepolymer (A) and azoles alkylamino formic acid ester compound (B) is that the equivalence ratio that the isocyanate group of carbamate prepolymer (A) and azoles alkylamino formic acid ester compound (B) active hydrogen atom that open loop produces in water contain base is NCO/H=0.4～4.0
With total composition during as 100 weight %, the amount of terephthalic acid particulate (C) is 0.05～20 weight %.
2, the moisture-curable carbamate composition of putting down in writing according to claim 1, wherein, containing the polyoxyalkylene chain that polyoxyalkylene chain, end have the carbamate prepolymer (A) of at least 2 isocyanate group in the molecule is polyoxybutylene chain and polyoxytrimethylene chain.
3, according to the moisture-curable carbamate composition of claim 2 record, wherein, carbamate prepolymer (A) contains polyoxybutylene chain 5～80 weight % and polyoxytrimethylene chain 20～95 weight %.
4, according to the moisture-curable carbamate composition of claim 1 record, wherein, terephthalic acid particulate (C) median size is 1～60 μ m.
5, according to the moisture-curable carbamate composition of claim 1 record, wherein, terephthalic acid particulate (C) is by polyoxyalkylene polyol and terephthalic acid being mixed, carrying out fragmentation with dispersion machine and obtain.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP038045/2003 | 2003-02-17 | ||
| JP2003038045A JP3714332B2 (en) | 2003-02-17 | 2003-02-17 | Moisture curable urethane composition |
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| CN1523066A CN1523066A (en) | 2004-08-25 |
| CN1330716C true CN1330716C (en) | 2007-08-08 |
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| CNB2004100049476A Expired - Fee Related CN1330716C (en) | 2003-02-17 | 2004-02-13 | Wet gas solidifying type carbamate composition |
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| JP (1) | JP3714332B2 (en) |
| KR (1) | KR100868528B1 (en) |
| CN (1) | CN1330716C (en) |
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| WO2008111323A1 (en) * | 2007-03-15 | 2008-09-18 | Dic Corporation | Moisture-curable urethane composition for waterproof material and urethane waterproof material |
| CN101376685B (en) * | 2007-08-30 | 2012-05-02 | 大日本油墨化学工业株式会社 | Two-solution curing type carbamate composition and construction method of water-proof structure |
| JP6892676B2 (en) * | 2017-01-10 | 2021-06-23 | オート化学工業株式会社 | Adhesive composition for wall material, wall structure to which adhesive composition for wall material is applied, and construction method of wall structure |
| CN111355192B (en) | 2018-12-20 | 2022-03-15 | 美利肯公司 | Multi-cavity inner conduit structure |
| CN112341601A (en) * | 2020-11-27 | 2021-02-09 | 苏州非特兄弟新材料科技有限公司 | Water removal agent and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001049225A (en) * | 1999-06-02 | 2001-02-20 | Sekisui Chem Co Ltd | Moisture-curing urethane adhesive composition and sealing composition |
| JP2001192637A (en) * | 2000-01-13 | 2001-07-17 | Sunstar Eng Inc | Moisture-curing one-pack type urethane adhesive composition |
| JP2002003566A (en) * | 2000-06-23 | 2002-01-09 | Dainippon Ink & Chem Inc | Urethane composition with moisture-curing property |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3399362B2 (en) * | 1998-05-21 | 2003-04-21 | 大日本インキ化学工業株式会社 | Moisture-curable urethane composition and coating material |
-
2003
- 2003-02-17 JP JP2003038045A patent/JP3714332B2/en not_active Expired - Lifetime
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2004
- 2004-02-12 KR KR1020040009361A patent/KR100868528B1/en active IP Right Grant
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001049225A (en) * | 1999-06-02 | 2001-02-20 | Sekisui Chem Co Ltd | Moisture-curing urethane adhesive composition and sealing composition |
| JP2001192637A (en) * | 2000-01-13 | 2001-07-17 | Sunstar Eng Inc | Moisture-curing one-pack type urethane adhesive composition |
| JP2002003566A (en) * | 2000-06-23 | 2002-01-09 | Dainippon Ink & Chem Inc | Urethane composition with moisture-curing property |
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|---|---|
| JP3714332B2 (en) | 2005-11-09 |
| JP2004244578A (en) | 2004-09-02 |
| KR100868528B1 (en) | 2008-11-12 |
| KR20040073979A (en) | 2004-08-21 |
| CN1523066A (en) | 2004-08-25 |
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