JPH07206965A - Polyurethane-based curable composition - Google Patents

Abstract

PURPOSE:To provide the subject composition containing an urethane prepolymer produced from a specific hydroxyl group-containing compound and an organic polyisocyanate compound, little in tackiness causing the surface staining of molded products, excellent in ordinary temperature curability, elongation, heat resistance and weatherability and suitable for sealing materials, etc. CONSTITUTION:This composition contains as an effective component an urethane prepolymer produced from (A) a hydroxyl group-containing compound and (B) an organic polyisocyanate compound such as tolylene diisocyanate. The hydroxyl group-containing compound comprises (a) a polyetherpolyol which is produced by addition-polymerizing an alkylene oxide to a di-or more-hydric active hydrogen compound in the presence of a cesium hydroxide as a catalyst and which has a number-average mol.wt. of >=2600 per hydroxyl group, a TU value satisfying an inequality I [y is the TU value (total unsaturation degree; unit: meq/g); x is a number-average mol.wt. per hydroxyl group] and a low mol. wt. component content satisfying an inequality II [W1 is the area a region having mol. wts. not larger than 1/4 of the number-average mol.wt. of the component (a) in a GPC chart; W2 is th whole area of the component (a) in the GPC chart] by a GPC analysis.

Description

Detailed Description of the Invention

[0001]

The present invention has a curability at room temperature,
Low tack that causes surface contamination, excellent elongation,
The present invention relates to a polyurethane-based curable composition which gives a cured product having tensile strength, heat resistance and weather resistance and is suitable as a coating / adhesive or filling composition such as a sealing material.

[0002]

BACKGROUND OF THE INVENTION Urethane prepolymers having an isocyanate group at the end are a one-pack type composition which cures by itself reacting with moisture in the atmosphere and a two-pack type composition which cures when mixed with a hydroxyl group-containing compound. It is used for things. These one-part or two-part compositions are sealing materials,
It is widely used in the field of construction materials such as waterproof materials and floor materials, and civil engineering materials.

[0003]

These polyurethane-based curable compositions are required to have heat resistance, weather resistance, low stain resistance and the like depending on their uses, but conventionally, various stabilizers and deterioration inhibitors have been added. However, satisfactory performance was not obtained. Further, a high molecular weight polyether polyol is required in order to obtain a sufficient elongation depending on the application, but it has been difficult to produce by conventional techniques.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventor has found that by using a polyether polyol having a high molecular weight and a low TU value,
It has been found that the polyurethane-based curable composition can be reduced in stain resistance and improved in elongation rate, tensile strength, heat resistance, and weather resistance. That is, the present invention provides a hydroxyl group-containing compound (A) comprising the following polyether-polyol (a)
A polyurethane-based curable composition containing, as an active ingredient, a urethane prepolymer composed of: and an organic polyisocyanate compound (B). Polyether polyol (a): Addition polymerization of an alkylene oxide to a divalent or higher valent hydrogen compound, the number average molecular weight per hydroxyl group is 2,600 or more, and the TU value satisfies the formula (1), G
A polyether polyol whose low molecular weight component content by PC analysis satisfies the formula (2). y ≦ 2 × 10 ⁻⁵ × x−0.015 (1) [where y is the TU value (total degree of unsaturation, unit meq / g),
x is the number average molecular weight per hydroxyl group] 0.07 ≧ W ₁ / W ₂ (2) [where W ₁ is the area of the region of ¼ or less of the number average molecular weight of (a) in the GPC chart, and W ₂ is (A) Total area in GPC chart]

In the present invention, the polyether polyol (a) is obtained by addition-polymerizing an alkylene oxide with a divalent or higher valent active hydrogen compound. The active hydrogen compound having a valence of 2 or more is, for example, a polyhydric alcohol (having a valence of 2 to 8 and a carbon number of 2).
~ 60 alcohols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane,
Castor oil, pentaerythritol, sorbitol and sucrose), amine compounds having 2 to 20 carbon atoms (eg octylamine, stearylamine, ethylenediamine, propylenediamine, toluenediamine and isophoronediamine), alkanolamines (eg monoethanolamine, monoisopropanolamine). , Diethanolamine and triethanolamine), carbon number 6-20
Polyphenols (for example, bisphenols), organic dicarboxylic acids having 4 to 40 carbon atoms (for example, phthalic acid, adipic acid, and dimer acid), compounds obtained by addition-polymerizing alkylene oxides with these compounds having active hydrogen of divalent or more. , And mixtures of two or more thereof. Of these, preferred is diethylene glycol,
Dipropylene glycol, glycerin and trimethylolpropane.

Examples of the alkylene oxide to be addition-polymerized to a divalent or higher valent active hydrogen compound include propylene oxide (hereinafter referred to as PO), ethylene oxide (hereinafter referred to as EO), 1,2-butylene oxide, tetrahydrofuran and styrene oxide. . Of these, mixed alkylene oxides containing PO, EO and PO are preferable, and PO is more preferable.

As the conditions applied to the addition polymerization reaction of alkylene oxide, the temperature is usually 50 to 150 ° C.,
It is preferably 70 to 110 ° C. The pressure of the reaction system with alkylene oxide is usually 1 to 8 kg / cm ² , preferably ² to 6 kg / cm ² .

The catalyst used in the addition polymerization reaction is
For example, metalloporphyrin (for example, Japanese Patent Publication No. 5-14734).
Japanese Laid-Open Patent Publication No. 63-2).
77236, JP-A-3-88821) and cesium hydroxide. Since a trace amount of catalyst remains in the polyether polyol, it may impair the curability of the polyurethane-based composition and may adversely affect the heat resistance and weather resistance of the cured product, making it easy to remove the catalyst after polymerization. In addition, cesium hydroxide is preferable because it has little effect even if a small amount remains.

The catalyst is usually added to the active hydrogen compound,
After dehydration treatment, alkylene oxide is added and polymerized,
The amount thereof is in the range of 0.005 to 2.0% by weight, preferably 0.05 to 1.5% by weight, based on the weight of the polyether polyol at the end of the polymerization.

As a method for purifying a crude polyether polyol obtained by polymerizing alkylene oxide, for example, an alkaline catalyst is neutralized with an acid described in JP-B-47-3745,
Method for removing generated salt by filtration, JP-A-53-12349
Method using an alkali adsorbent disclosed in JP-B-9, JP-B-49-
The method of dissolving in a solvent of JP-A-14359 and washing with water, the method of using an ion exchange resin of JP-A-51-23211, and the carbonic acid formed by neutralizing the alkaline catalyst of JP-B-52-33000 with carbon dioxide gas. There is a method of filtering the salt and the like, and any of them may be used. Among these, the method using an alkali adsorbent and the method of washing with water are preferable, and the method using an alkali adsorbent is particularly preferable.

In the present invention, the number average molecular weight of the polyether polyol (a) obtained by addition-polymerizing an alkylene oxide to a divalent or higher-valent active hydrogen compound is usually 2,600 or more per hydroxyl group, and preferably 3, 000
That is all. If it is less than 2,600, sufficient elongation cannot be obtained.

In the present invention, the TU value of the polyether polyol (a) satisfies the formula (1). y ≦ 2 × 10 ⁻⁵ × x−0.015 (1) [where y is TU value (meq / g), x is number average molecular weight per hydroxyl group] When the TU value is large, the content of monool is Since it increases, the crosslinking reaction in the polyurethane-forming reaction is stopped in the middle to inhibit the increase in molecular weight, so that the resin physical properties of the cured product, such as elongation, heat resistance, weather resistance, and low stain resistance, are reduced.

In the present invention, the content of the low molecular weight component in the polyether diol (a) by GPC analysis is an amount satisfying the following formula (2). 0.07 ≧ W ₁ / W ₂ (2) [where W ₁ is the area of the region of ¼ or less of the number average molecular weight of (a) in the GPC chart, and W ₂ is the area of the entire (a) in the GPC chart. ] When the content of the low molecular weight component is high, a tack that causes surface contamination is strong and a cured product having a low elongation is provided.

In the present invention, the proportion of (a) in (A) in the polyurethane-based curable composition is usually 60% or more, preferably 70% or more, based on the hydroxyl group equivalent.
If it is less than 60%, heat resistance, weather resistance, stain resistance, elongation, etc. will be insufficient.

The hydroxyl group-containing compound (A) other than (a) in the present invention means that the number average molecular weight per hydroxyl group is 2,6.
It is a compound containing less than 00 and having two or more hydroxyl groups, and is, for example, a polyhydric alcohol (2 to 8 valent carbon atoms 2 to 60).
Alcohols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, castor oil, pentaerythritol, sorbitol and sucrose), and compounds obtained by addition-polymerizing alkylene oxide with these compounds, having 2 to 2 carbon atoms. Compounds obtained by addition-polymerizing alkylene oxides to 20 amine compounds (eg, octylamine, stearylamine, ethylenediamine, propylenediamine, toluenediamine and isophoronediamine), alkanolamines (eg, monoethanolamine, monoisopropanolamine, diethanolamine and triethanol). Compounds obtained by addition-polymerizing alkylene oxides to amines, polyphenols having 6 to 20 carbon atoms (for example, Compounds obtained by addition polymerization of alkylene oxide to bisphenol), carbon atoms 4 to 40
And organic dicarboxylic acids (for example, phthalic acid, adipic acid and dimer acid) obtained by addition-polymerizing an alkylene oxide, and a mixture of two or more thereof. Of these, preferred are compounds obtained by addition-polymerizing alkylene oxides with diethylene glycol, dipropylene glycol, glycerin and trimethylolpropane.

In the present invention, the organic polyisocyanate compound is an aromatic, alicyclic or aliphatic isocyanate compound having two or more isocyanate groups (hereinafter referred to as NCO groups), a mixture of two or more thereof, and There is a modified polyisocyanate compound obtained by modifying them. Specific examples thereof include polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate (commonly known as crude MDI), xylylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate, and prepolymer modified products thereof. Of these, tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate are preferred.

The polyurethane-based curable composition is classified into a one-pack type composition which is cured by reacting with moisture in the air alone and a two-pack type composition which is cured by mixing with a hydroxyl group-containing compound. All of them require the production of a urethane prepolymer having an NCO group at the end.

The urethane prepolymer having an NCO group at the terminal can be produced from the hydroxyl group-containing compound (A) and the organic polyisocyanate compound (B). (A) and (B)
The ratio of (B) / (A) is usually 1.5 to 3.
5, preferably 1.8 to 3.0. The reaction is usually carried out by adding the component (B) to the component (A) adjusted to have a water content of 0.1% or less, preferably 0.03% or less, and usually 50 to 150%.
Stirring is performed in a nitrogen atmosphere at a temperature range of 2 to 12 hours.
The order of preparation of (A) and (B) may be such that (B) is added to (A) or vice versa. A solvent may be added if necessary. The solvent may be added after the reaction is completed or before the reaction is started. The amount of the solvent added is usually 30% by weight or less, preferably 15% by weight or less, based on the total weight of (A) and (B).

The free NCO group content (% by weight) of the urethane prepolymer is usually 0.2 to 6.0%, preferably 0.5 to 4.0%, based on the total weight of (A) and (B). Is.

The two-pack type curable composition comprises a urethane prepolymer and a curing agent containing a hydroxyl compound capable of cross-linking and polymerizing the terminal NCO groups. The composition of the curing agent is the hydroxyl group-containing compound (A), Examples include a catalyst for accelerating curing and, if necessary, a reinforcing agent, a filler, a plasticizer, a pigment, an anti-sagging agent, and the like.

The one-pack type moisture-curable composition is one in which the terminal NCO groups of the urethane prepolymer are cross-linked and polymerized by the moisture in the air. If necessary, a catalyst and a reinforcing agent for the curing acceleration, a filler, a A plasticizer, a pigment, an anti-sagging agent, etc. may be contained.

Examples of the catalyst for accelerating curing which can be used in the present invention include alkyl titanates, organic silicon titanates, metal salts of carboxylic acids such as tin 2-ethylhexylate and dibutyltin dilaurate, and dibutylamine-2. -Examples include amine salts such as ethylhexoate. Among these, tin 2-ethylhexylate and dibutyltin dilaurate are preferable. The addition amount is 1.0% by weight or less, preferably 0.01 to 0.5% by weight in the polyurethane curable composition.

Examples of the reinforcing agent, filler, plasticizer, pigment, anti-sagging agent, solvent and the like that can be used in the present invention include the following. Examples of the reinforcing agent include carbon black, finely powdered silica, and resin acid-treated calcium carbonate, and the addition amount is 50% by weight or less, preferably 5 to 30% by weight in the polyurethane curable composition. Examples of the filler include calcium carbonate, talc, clay, silica and the like, and the addition amount is 50% by weight or less, preferably 1 in the polyurethane curable composition.
It is 0 to 40% by weight. As the plasticizer, dioctyl phthalate, dibutyl phthalate, dioctyl adipate,
Chlorinated paraffin and petroleum-based plasticizers may be used, and the addition amount is 20% by weight or less, preferably 10% by weight or less in the polyurethane curable composition. Examples of the pigment include inorganic pigments such as iron oxide, chromium oxide, and titanium oxide, and organic pigments such as phthalocyanine blue and phthalocyanine green. The addition amount is 5% by weight or less in the polyurethane-based curable composition, preferably It is 3% by weight or less. Examples of the anti-sagging agent include organic acid-treated calcium carbonate, hydrogenated castor oil, calcium stearate, aluminum stearate, zinc stearate, and fine powder silica. The addition amount is 5% by weight in the polyurethane-based curable composition. % Or less, preferably 2% by weight or less. As the solvent, aromatic compounds (toluene, xylene, etc.), aliphatic compounds or alicyclic compounds (n-hexane, cyclohexane, etc.), ketone compounds (methyl ethyl ketone, methyl isobutyl ketone, etc.), ester compounds (ethyl acetate, butyl acetate, etc.) ) And ether ester (ethyl cellosolve acetate, butyl cellosolve acetate, etc.), and the addition amount is 1 in the polyurethane-based curable composition.
It is 0% by weight or less, preferably 5% by weight or less. Further, an antioxidant and an ultraviolet absorber can be used as well.
The addition amount is 3% by weight or less, preferably 1% by weight or less in the polyurethane curable composition.

[0024]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. The parts in the production examples, examples and comparative examples are parts by weight.

Production Example 1 125 parts of a dipropylene glycol / PO adduct, a polymer having a number average molecular weight of 1,000 as an active hydrogen compound in an autoclave, cesium hydroxide (50% aqueous solution, reagent grade, the same applies hereinafter) 16 All parts were charged and stirred under reduced pressure at 120 ° C. to uniformly dissolve and dehydrate. Next, after the system was adjusted to 0 to 10 mmHg at 100 ° C., 875 parts of PO was continuously introduced so that the gauge pressure was maintained at about 4 to 6 kgf / cm ² . Then, the mixture was aged at the same temperature for about 8 hours to obtain a crude polyether. As a result of analysis after the adsorbent treatment, the TU value was 0.
The value was 046 meq / g, the hydroxyl value was 16.0, the low molecular weight component content was 0.057, and the number average molecular weight converted from the hydroxyl value was 7,012. The TU value and the hydroxyl value were measured according to the following (the same applies hereinafter). The obtained polyether compound is called polyether A. Hydroxyl value measuring method: JISK-1557-1970 (phthalic anhydride / pyridine method) TU value measuring method: ASTMD-2849-69 (mercuric acetate method)

Production Example 2 Glycerin / as an active hydrogen compound was added to an autoclave.
185 with PO adduct, polymer with number average molecular weight of 1,000
And 16 parts of cesium hydroxide were added and stirred at 120 ° C. under reduced pressure to uniformly dissolve and dehydrate. Then, after setting the inside of the system to 0 to 10 mmHg at 100 ° C., 815 parts of PO was continuously introduced so as to maintain the gauge pressure at about 4 to 6 kgf / cm ² . Then, the mixture was aged at the same temperature for about 6 hours to obtain a crude polyether. As a result of the analysis after the adsorbent treatment, the TU value was 0.026 meq / g, the hydroxyl value was 33.6, the low molecular weight component content was 0.042, and the number average molecular weight converted from the hydroxyl value was 5,009. The resulting polyether compound is called polyether B.

Production Example 3 As an active hydrogen compound, 235 parts of a dipropylene glycol / PO adduct, a polymer having a number average molecular weight of 1,000, and 16 parts of cesium hydroxide were added to an autoclave to obtain 12
The mixture was stirred at 0 ° C. under reduced pressure to uniformly dissolve and dehydrate. Then, the system was adjusted to 0 to 10 mmHg at 100 ° C., and then 765
Part of PO was continuously introduced so that the gauge pressure was kept at about 4 to 6 kgf / cm ² . Then, the mixture was aged at the same temperature for about 8 hours to obtain a crude polyether. As a result of the analysis after the adsorbent treatment, the TU value was 0.020 meq / g, the hydroxyl value was 28.0,
The low molecular weight component content was 0.033, and the number average molecular weight converted from the hydroxyl value was 4,007. The obtained polyether compound is called polyether C.

Example 1 Mixture of 670 parts of polyether A and 265 parts of polyether B 2,4- and 2,6-tolylene diisocyanate [2,4- / 2,6-ratio of 80 / 20, trade name T-80, manufactured by Nippon Polyurethane Industry Co., Ltd.] 65 parts were added, and stirring was continued at 80 ° C. for 7 hours in a closed reaction vessel under a nitrogen atmosphere, and a urethane having a free NCO group content of 1.65%. A prepolymer was obtained. This urethane prepolymer 10
Dioctyl phthalate 30 as a plasticizer for 0 part
Parts, 60 parts of a resin acid-treated calcium carbonate as a reinforcing agent, and 10 parts of titanium oxide as a pigment were added and mixed in a kneader to obtain a homogeneous one-pack type polyurethane curable composition. The above composition was moisture-cured at 25 ° C. for 7 days, about 1.0 m
Table 1 shows the initial physical properties and surface stain resistance of the m-thick completely cured sheet, the physical properties after heating the same at 80 ° C. for 7 days, and the physical properties after exposure to a sunshine weatherometer for 500 hours. The surface stain resistance was evaluated based on the weight of silica sand remaining on the sheet after the sand was shaken off after spraying No. 7 silica sand on the sheet.

Example 2 600 parts of polyether A, 150 parts of polyether B and Sannix diol PP-2000 [manufactured by Sanyo Kasei Co., Ltd., diprolene glycol / PO adduct, T
U value 0.019, OH number 56.1, low molecular weight component content 0.035, number average molecular weight 2,000] To a mixture of 170 parts, 80 parts of T-80 was added, and the mixture was placed in a closed reaction vessel under a nitrogen atmosphere. At 80 ° C., stirring was continued for 6 hours to obtain a urethane prepolymer having a free NCO group content of 2.00%, which was used as a main component. On the other hand, polyether A / polyether B = 3
/ 2 (weight ratio) 120 parts, resin acid treated calcium carbonate 1
00 parts, 25 parts of titanium oxide and 5 parts of lead 2-ethylhexylate (lead content 19%) were mixed in a kneader to obtain a homogeneous paste-like dispersion, which was used as a curing agent. 100 parts of the main agent and 250 parts of the curing agent are sufficiently mixed to form a sheet having a thickness of about 1.5 mm and cured at 25 ° C. for 7 days and further at 50 ° C. for 1 day to obtain a completely cured sheet. Obtained. This sheet was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 1 250 parts of polyether B and Sannix diol PP-4000 [Sanyo Chemical Co., Ltd. product, diprolene glycol / PO adduct, TU value 0.094, OH value 2
8.0, low molecular weight component content 0.103, number average molecular weight 4,007] 84 parts T-80 to a mixture of 666 parts, and stirred at 80 ° C. for 7 hours in a closed reaction vessel under nitrogen atmosphere. Was continued to obtain a urethane prepolymer having a free NCO group content of 2.10%. This urethane prepolymer 100
Dioctyl phthalate 40 as a plasticizer for parts
Parts, 50 parts of a resin acid-treated calcium carbonate as a reinforcing agent, and 10 parts of titanium oxide as a pigment were added and mixed with a kneader to obtain a homogeneous one-pack type polyurethane curable composition. A moisture-cured completely cured sheet having a thickness of about 1.0 mm was obtained. This sheet was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 2 250 parts of polyether B and 66 parts of polyether C
84 parts of T-80 was added to the mixture of 6 parts, and the mixture was stirred under a nitrogen atmosphere in a closed reaction vessel at 80 ° C. for 7 hours to give free NC.
A urethane prepolymer having an O group content of 2.10% was obtained.
To 100 parts of this urethane prepolymer, 40 parts of dioctyl phthalate as a plasticizer, 50 parts of resin acid treated calcium carbonate as a reinforcing agent, and titanium oxide of 10 as a pigment.
Parts were added and mixed with a kneader to obtain a homogeneous one-pack type polyurethane curable composition. A moisture-cured completely cured sheet having a thickness of about 1.0 mm was obtained. This sheet was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 3 70 parts of T-80 was added to a mixture of 400 parts of polyether A, 250 parts of polyether B and 280 parts of polyether C, and the mixture was added in a closed reaction vessel at 80 ° C. under a nitrogen atmosphere. The stirring was continued for 7 hours to obtain a urethane prepolymer having a free NCO group content of 1.70%. To 100 parts of this urethane prepolymer, 30 parts of dioctyl phthalate as a plasticizer and 60 parts of a resin acid treated calcium carbonate as a reinforcing agent
Parts and 10 parts of titanium oxide as a pigment were added and mixed with a kneader to obtain a homogeneous one-pack type polyurethane curable composition. The above composition was moisture-cured at 25 ° C. for 7 days, and the initial physical properties and surface stain resistance of a completely cured sheet having a thickness of about 1.0 mm, physical properties after heating the composition at 80 ° C. for 7 days, and sunshine were obtained. Table 1 shows the physical properties after exposure to a weatherometer for 500 hours.

[0033]

The polyurethane-based curable composition of the present invention is composed of a polyether polyol having a number average molecular weight per hydroxyl group of 2,600 or more and a low content of low molecular weight components, and therefore has a particularly large elongation. It is also suitable as a sealing material because it has a low stress of 100%.
Since the value is extremely low, it is particularly excellent in stain resistance, and also has good heat resistance and weather resistance, and is industrially very useful as a composition for coating / adhesion or filling.

[Table 1]

Claims (7)

[Claims] 1. A polyurethane-based curable composition containing, as an active ingredient, a urethane prepolymer consisting of a hydroxyl group-containing compound (A) consisting of the following polyether polyol (a) and an organic polyisocyanate compound (B). Polyether polyol (a); number-average molecular weight per hydroxyl group is 2,600 or more and TU value is determined by addition-polymerizing an alkylene oxide with a divalent or higher valent active hydrogen compound, and TU value is determined by formula (1), and GPC analysis is performed. The polyether polyol having a low molecular weight component content according to the formula (2). y ≦ 2 × 10 ⁻⁵ × x−0.015 (1) [where y is the TU value (total degree of unsaturation, unit meq / g),
x is the number average molecular weight per hydroxyl group] 0.07 ≧ W ₁ / W ₂ (2) [where W ₁ is the area of the region of ¼ or less of the number average molecular weight of (a) in the GPC chart, and W ₂ is (A) Total area in GPC chart] 2. The (A) of (a) based on the number of hydroxyl groups.
The polyurethane-based curable composition according to claim 1, which has a ratio to 70% or more. 3. The polyurethane curable composition according to claim 1, wherein (a) is obtained by addition-polymerizing an alkylene oxide to a divalent or higher valent active hydrogen compound using cesium hydroxide as a catalyst. 4. The curable polyurethane composition according to claim 3, wherein the amount of cesium hydroxide is 0.05 to 1.5% by weight in (a) at the end of the polymerization. 5. The polyurethane-based curable composition according to claim 1, wherein the alkylene oxide is propylene oxide or a mixed alkylene oxide containing propylene oxide. 6. The polyurethane curable composition according to claim 1, further comprising (A) as a curing agent added to the urethane prepolymer. 7. A coating / adhesive or filling composition comprising the polyurethane curable composition according to claim 1.