Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – At least one aryl ring which is part of a fused or bridged...
Reexamination Certificate
1999-10-18
2001-01-30
Niland, Patrick D. (Department: 1714)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
At least one aryl ring which is part of a fused or bridged...
C524S115000, C524S123000, C524S130000, C524S133000, C524S136000, C524S147000, C524S154000, C524S589000, C528S051000, C528S052000, C528S053000, C528S044000
Reexamination Certificate
active
06180713
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a one-pack type moisture curable urethane composition suitable for use as, for example, a sealing agent for automobiles, buildings and structures, an adhesive, and a coating agent. More specifically, it relates to a one-pack type moisture curable urethane composition having an excellent storage stability in the absence of moisture without decreasing a catalyst activity and having a sufficient curability with atmospheric moisture.
BACKGROUND ART
To ensure the storage stability of curable urethane compositions, especially one-pack type moisture curable urethane compositions, malonate compounds such as diethyl malonate (DEM), dimethyl malonate (DMM), isopropyl malonate (IPM), etc. have been heretofore used. However, when the malonate compounds are used, in the presence of an isocyanate group, together with a relatively highly active catalyst having a structure such as a dimethylamino group, the catalyst activity is decreased. Therefore, there are problems that only catalysts having extremely limited structure such as those having a morpholine structure can be used. For this reason, since a large amount of catalysts having a relatively weak activity such as morpholine-based catalysts, etc. should be used, the use of the one-pack type moisture curable urethane compositions is extremely limited from the viewpoints of, for example, the curability characteristics and high cost.
DISCLOSURE OF INVENTION
Accordingly, the objects of the present invention are to provide a one-pack type moisture curable urethane composition capable of increasing the storage stability thereof without decreasing the catalyst activity even when amine catalysts having, for example, a dimethylamino group structure having a high catalytic activity are used.
In accordance with the present invention, there is provided a one-pack type moisture curable urethane composition comprising a urethane prepolymer and an amine catalyst and 0.002 to 50 parts by weight, based upon 100 parts by weight of the urethane prepolymer, of at least one storage stabilizer selected from the group consisting of phosphonic ester compounds, phosphonous ester compounds, phosphinous ester compounds and phosphines.
BEST MODE FOR CARRYING OUT THE INVENTION
According to the present invention, as mentioned above, the storage stability of the one-pack type moisture curable urethane composition can be increased, without impairing the activity of the amine catalysts by compounding thereinto phosphonic ester compounds, phosphophonous ester compounds, phosphinous ester compounds or phosphine compounds or any mixtures thereof. Thus, when phosphonic ester compounds, phosphonous ester compounds, phosphinous ester compounds or phosphine compounds or any mixtures thereof are used as a storage stabilizer for a one-pack type moisture curable urethane composition, the use of a catalyst having a structure such as a dimethylamino group becomes possible, various curability phenomena can be selected and a catalyst having a high activity can be used. As a result, the use of the composition becomes advantageous from the viewpoints of the cost.
The urethane prepolymers formulated into the urethane composition according to the present invention are known substances and include, for example, polyether polyols having a desired isocyanate functionability of 2.2-3.0 obtained by reacting 4,4′-diphenylmethane diisocyanate to a mixture of a polyol component such as polyetherpolyol having 3 or more hydroxyl group per molecule, e.g., polyoxypropylene triol, polyoxyethylene triol and a diol component such as polyether diol having 2 hydroxyl group per molecule, e.g., polypropylene ether diol, polyethylene ether diol. The preferable urethane prepolymers are those obtained by reacting mixtures of polyether triols having a number average molecular weight of 1000-7000, preferably 4000-6000 and polyether diols having a number average molecular weight of 1000-3000, preferably 1500-2500, with 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, etc., in such a manner that an equivalent ratio of NCO/OH becomes 1.1-2.5, preferably 1.5-1.9.
The curing catalysts usable in the present invention are amine catalysts generally used in the one-pack type moisture curable urethane composition, such as, for example, dimorpholinodiethyl ether, N,N-dimethylcyclohexyl amine, N,N-dimethylaminoethyl morpholine, bis(2-dimethylaminoethyl)ether, N-methylmorpholine, triethylenediamine, 1-isobutyl-2-methylimidazol, N,N′-dimethyl piperazine, pentamethyldiethyl triamine, etc. Although there are no specific limitations to the amounts of the catalyst, the preferable amount is 0.002-10 parts by weight, more preferably 0.02-6 parts by weight, based upon 100 parts by weight of the urethane prepolymer.
The one-pack type moisture curable polyurethane compositions according to the present invention include, as a storage stabilizer, 0.002-50 parts by weight, preferably 0.005-3 parts by weight, based upon 100 parts by weight of the urethane prepolymer, of phosphonic ester compounds, phosphonous ester compounds, phosphinous ester compounds and/or phosphine compounds. When the formulating amount of the phosphonic ester compounds, phosphonous ester compounds, phosphinous ester compounds and/or phosphine compounds is too small, the storage stability and the catalyst deactivation cannot be unpreferably suppressed, whereas when the amount is too large, the decrease in the properties after the curing becomes unpreferably remarkable.
The phosphonic ester compounds, phosphonous ester compounds, phosphinous ester compounds and/or phosphine compounds usable, as a storage stabilizer, in the present invention include, for example, organic phosphorous compounds having the formula:
R
n
—P—(—OR)
3-n
wherein R represents a univalent or bivalent linear or cyclic organic group and n is an integer of 0-3.
Examples of the phosphonic ester compounds usable in the present invention are triphenyl phosphite, tris(nonylphenyl) phosphite, triethyl phosphite, triisopropyl phosphite, triisobutyl phosphite, tridecyl phosphite, triisodecyl phosphite, tris(tridecyl)phosphite, tri(2-ethylhexyl)phosphite, diphenylmono(2-ethylhexyl)phosphite, diphenylmonodecyl phosphite, diphenylmono(tridecyl)phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, tetraphenyl dipropylene glycol diphosphite, tetraphenyl tetra(tridecyl)pentaerythritol tetraphosphite, tetra(tridecyl)-4,4′-isopropylidene diphenyldiphosphite, trilauryltrithio phosphite, bis(tridecyl)pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, tris(2,4-di-t-butylphenyl) phosphite, tricyclohexyl phosphite, dicyclohexyl-2,4-di-t-butylphenyl phosphite, hydrogenated bisphenol A-pentaerythritol phosphite polymer, hydrogenated bisphenol A phosphite polymer, etc.
The phosphonous ester compounds usable in the present invention include phenyl phosphonous diethyl ester, 2-phenyl-1,3,2-dioxaphosphorun, etc. The phosphinous ester compounds include diphenylphosphinous ethyl ester, diphenylphosphinous butyl ester, etc.
Examples of the phosphine compounds usable in the present invention are triphenyl phosphine, triorthotolyl phosphine, trimethatolyl phosphine, triparatolyl phosphine, tris-4-methoxyphenyl phosphine, diphenylcyclohexyl phosphine, dicyclohexylphenyl phosphine, tricyclohexyl phosphine, trioctyl phosphine, tributyl phosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, tribenzylphosphine, etc.
The one-pack type moisture curable urethane composition according to the present invention may further contains, in addition to the above-mentioned essential components, fillers, plasticizers, solvents, etc., which are inactive to the isocyanate group, to impart the desired properties, etc. Examples of the fillers are carbon blacks, clays, talcs, calcium carbonate, etc. or any mixture thereof. Examples of the plasticizers are phthalic acid derivatives such as dibutyl phthalate, dioctyl
Araki Kiminori
Ishikawa Kazunori
Finnegan Henderson Farabow Garrett & Dunner L.L.P.
Niland Patrick D.
The Yokohama Rubber Co. Ltd.
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