JPH11116652A - Moisture-curable urethane resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a moisture-curable urethane resin composition excellent in weather resistance, having good reactivity with moisture and especially useful as an adhesive composition for building, a sealing agent composition and a composition for coating materials. SOLUTION: This urethane resin composition comprises a urethane prepolymer having an active isocyanate group capable of reacting with water content in air, and the urethane prepolymer having the active isocyanate group comprises at least 2,5 and/or 2,6-diisocyanate-methylbicyclo[2,2,1]heptane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a moisture-curable urethane resin composition, which comprises 2,5 and / or 2,6-diisocyanatomethylbicyclo [2,2,1] heptane (hereinafter referred to as NBDI) as an organic isocyanate component. Abbreviated as an essential component, and appropriately mixing a urethane prepolymer composition obtained by reacting the component with a component having one or more active hydrogen groups in one molecule to obtain a weather resistance. The present invention relates to a moisture-curable urethane resin composition having excellent moisture resistance and good reactivity with moisture. Specifically, the composition is used as an adhesive for architects requiring a design property, such as an adhesive for jointless exterior tiles, a sealing agent for a portion requiring weather resistance such as a window frame, and a coating agent for a repair paint. It relates to useful compositions.

[0002]

2. Description of the Related Art Urethane prepolymers having active isocyanate groups are widely used as moisture-curable compositions such as building adhesives, sealing agents and coating agents. In particular, for building adhesives and sealing agents,
2,4 and / or 2,6 as an organic isocyanate component
An aromatic isocyanate such as tolylene diisocyanate (hereinafter sometimes abbreviated as TDI), 4,4 and / or 2,4-diphenylmethane diisocyanate (hereinafter sometimes abbreviated as MDI), and activity of a glycol component or the like; It is often produced by reacting with a compound having hydrogen. A filler component, a plasticizer, a solvent, an additive, and the like are added to the urethane prepolymer as needed to obtain a moisture-curable composition.

[0003]

In recent technical trends, weather resistance may be required for not only coating agents but also architectural adhesives and sealing agents depending on the use. For example, a sealing agent used for fixing a window glass must be weather-resistant because it is constantly exposed to the outside. Recently, a construction method using an organic adhesive, particularly a one-component moisture-curable adhesive, instead of mortar for bonding exterior tiles has been developed. Normally, tiles are filled with mortar called joints between the tiles, but the adhesive is directly exposed between the tiles without filling the joints to enhance the design of the outer wall and give a sense of quality It is a construction method. Since there is no joint filling work, labor costs can be reduced, the construction period can be shortened, and construction costs can be reduced. In addition, in the conventional construction method, even when filling joints, a method of replacing the conventional joint agent from cement / mortar with a sealing agent has been proposed. In these cases, a part of the sealing agent or the adhesive is exposed to sunlight or wind and rain, so that the agent is newly required to have weather resistance. However, in both methods as described above, the aromatic isocyanate used for the urethane prepolymer which is a resin component used in the conventional sealing agent and adhesive is generally called yellowing isocyanate, Exposure to the components causes a significant yellowing, which not only deteriorates the appearance, but also impairs the original function due to the deterioration (see “Photodeterioration and stabilization of polymers”, Chapter 6 4 Published by CMC Corporation). For applications requiring such weather resistance, a method for producing a urethane prepolymer using an alicyclic or aliphatic isocyanate generally called a non-yellowing isocyanate (JP-A-52-52997) is employed. However, due to the low reactivity caused by the non-yellowing isocyanate, the reaction with moisture does not proceed promptly, and the initial curability, which is a property strictly required for the use, is poor.
There is a problem that a product having satisfactory performance as an adhesive, a sealing agent, and a coating agent cannot be obtained.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, as an organic isocyanate, 2,5 and / or 2,6-diisocyanatomethylbicyclo [2,2,1] heptane was used. Is excellent in weather resistance and reacts with moisture by making a urethane prepolymer obtained by reacting an organic isocyanate containing as an essential component with an active hydrogen compound having one or more active hydrogen groups in one molecule. It has been found that a moisture-curable urethane resin composition having good properties can be obtained, and the present invention has been completed. In the present invention, the ratio of the number of isocyanate groups (A) of all the organic isocyanate compounds to the number of active hydrogen groups (B) of all the active hydrogen compounds to be used, A / B is 1.2 or more and 10 or less. It is more preferable to mix them. In the present invention, a catalyst is added as required, and the mixture is reacted at 30 ° C. to 120 ° C. to obtain a moisture-curable urethane prepolymer. Further, by appropriately blending the obtained moisture-curable urethane prepolymer with an extender pigment, a plasticizer, a solvent, an additive, and the like as necessary, the moisture is excellent in weather resistance and has good reactivity with moisture. It is a curable urethane resin composition.

That is, the present invention provides the following (1) to
(9) is provided. (1) A moisture-curable urethane resin composition comprising a urethane prepolymer having an active isocyanate group capable of reacting with moisture in the air, wherein the organic isocyanate having the active isocyanate group contains at least 2,5 and / or
Or 2,6-diisocyanatomethylbicyclo [2,
[2,1] A moisture-curable urethane resin composition comprising heptane. (2) The content of 2,5 and / or 2,6-diisocyanatomethylbicyclo [2,2,1] heptane in all organic isocyanates used for the urethane prepolymer is as follows:
The moisture-curable urethane resin composition according to (1), which is 20 to 100% by weight.

(3) A urethane prepolymer is obtained by reacting an organic isocyanate having two or more isocyanate groups in one molecule with an active hydrogen compound having one or more active hydrogen groups in one molecule. The moisture-curable urethane resin composition according to (1) or (2), wherein: (4) The ratio (A / B) of the number (A) of the isocyanate groups of the organic isocyanate to the number (B) of the active hydrogen groups of the active hydrogen compound is from 1.2 to 10 ( 3) The moisture-curable urethane resin composition according to the above.

(5) A moisture-curable urethane resin composition characterized by using a urethanizing catalyst when producing the urethane prepolymer according to (3) or (4). (6) The reaction temperature for producing the urethane prepolymer according to any one of (3) to (5) is 30 to 120 ° C.
A moisture-curable urethane resin composition, characterized in that:

(7) A moisture-curable adhesive composition comprising the moisture-curable urethane resin composition according to any one of (1) to (6) as a main component. (8) A moisture-curable sealing agent composition comprising the moisture-curable urethane resin composition according to any one of (1) to (6) as a main component. (9) A composition for a moisture-curable coating composition comprising the moisture-curable urethane resin composition according to any one of (1) to (6) as a main component.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The moisture-curable urethane prepolymer used in the present invention includes an organic isocyanate having an active isocyanate group capable of reacting with moisture in the air, and at least as an organic isocyanate component having the active isocyanate group, 2,5 and / or 2,6
-Diisocyanatomethylbicyclo [2,2,1] heptane as an essential component. In the present invention,
2,5 and / or 2,6-diisocyanatomethylbicyclo [2,2,1] heptane may be used alone or in combination with other organic isocyanate components.
In the case of combined use, 2,5 and / or 2,6-
The content of diisocyanatemethylbicyclo [2,2,1] heptane is used in the range of 20 to 100% by weight of the total organic isocyanate. Preferably, it is in the range of 50 to 100% by weight, more preferably 70 to 100% by weight. When the content of 2,5 and / or 2,6-diisocyanatomethylbicyclo [2,2,1] heptane is less than 20% by weight, reactivity with moisture, which is a characteristic of this compound, is impaired, When used as an adhesive, a coating material, or a sealing material, the moisture curing reaction tends to be slow, which is not preferable.

The other organic isocyanate component used in the present invention is preferably an organic isocyanate having two or more active isocyanate groups in one molecule. Specifically, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, phenylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4′-diisocyanate, naphthylene-1,5-diisocyanate, hexamethylene diisocyanate, Isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane-4,4′-diisocyanate, and the like. These other organic isocyanates may be used alone or in combination of two or more.

The active hydrogen compound having one or more active hydrogen groups in one molecule used in the present invention includes, for example, methanol, ethanol, 1-isopropyl alcohol, butanol, 2-butanol, and the like. Alcohols such as t-butanol, ricinoleic acid, hydroxyl-containing fatty acids such as dehydrated castor oil, ethylene glycol, propylene glycol, butanediol, hexanediol, diethylene glycol, glycerin, hexanetriol, trimethylolpropane, pentaerythritol, polyethylene glycol, and polypropylene Glycol, polytetramethylene glycol, polyester polyol, polyoxypropylene diol, polyoxypropylene triol, polycarbonate diol, acrylic polyol, etc. Glycols, ethanolamine,
Propanolamine, dimethylethanolamine, dimethylpropanolamine, ethylenediamine, hexamethylenediamine, amines such as γ-aminopropyltriethoxysilane and the like, and these alone or
Two or more kinds may be used in combination.

In the present invention, when producing a urethane prepolymer, a urethanization catalyst which is added and used as necessary includes metal catalysts such as dibutyltin dilaurate and lead octylate, triethylamine, N, N- (dimethyl). Tertiary amines such as aminoethyl) morpholine; The amount used is 0.001 to 0.1% by weight, preferably 0.002 to 0.05% by weight, more preferably 0.003 to 0% by weight, based on 100% by weight of the urethane prepolymer. 0.01% by weight.
If the amount is less than 0.001% by weight, there is a tendency that a sufficient effect for promoting the urethanization reaction is not obtained. If the amount exceeds 0.1% by weight, the urethanization reaction becomes too fast, and In this case, it is not possible to control heat generation at the time, a side reaction occurs due to thermal runaway, and gelation occurs, and a desired urethane resin tends to be not obtained.

The method for producing the moisture-curable urethane resin composition of the present invention is not particularly limited, but
In a preferred embodiment, the organic hydrogen compound is produced by reacting the organic isocyanate compound (A) containing 2,5 and / or 2,6-diisocyanatomethylbicyclo [2,2,1] heptane with the active hydrogen-containing compound (B). This is an example. When reacting the above compound, the ratio of the number (A) of isocyanate groups of the organic isocyanate to the number (B) of active hydrogen groups of the active hydrogen compound, that is, A / B is 1.2 or more and 10 or less. To mix. The mixing ratio is preferably in the range of 1.2 to 8, and more preferably in the range of 1.2 to 7. At this time, if the compounding ratio (A / B) is less than 1.2, the viscosity in the system is remarkably increased, and there is a tendency that a problem at the time of production tends to occur such that it is impossible to take out from the reactor. If the compounding ratio exceeds 10, the active isocyanate group in the system increases, and a large amount of carbon dioxide gas is generated by the reaction with moisture, and is added to the adhesive composition, sealer composition, and coating composition later. When used as such, there is a tendency that problems such as a decrease in strength and deterioration of appearance are likely to occur. Further, at the time of the reaction, the above-mentioned urethanization catalyst is added at 0.001% or more and 0.1% or less as needed. Further, the reaction is performed at a reaction temperature of 30 ° C. to 120 ° C. when the above reaction is performed,
The reaction is performed until almost all active hydrogen groups in the system have reacted.
The reaction temperature is preferably in the range of 40 to 110 ° C, more preferably 50 to 90 ° C. Temperature 30
When the temperature is lower than 0 ° C, the reaction between the isocyanate group and the active hydrogen group does not proceed rapidly, and the reaction time tends to be extremely long. When the temperature is higher than 120 ° C, the urethane-forming reaction is remarkably accelerated, thereby generating heat. Uncontrollable, a reaction other than the urethane reaction occurs, the viscosity in the system increases significantly,
As a result, gelation tends to occur, which is also not preferable.

The moisture-curable adhesive composition containing the moisture-curable urethane resin composition of the present invention as a main component means that the moisture-curable urethane resin contains an extender, a plasticizer, a solvent, an additive, a colorant, etc. It is obtained by mixing and kneading these using a high-viscosity stirrer such as a planetary mixer.

The extender used herein includes calcium carbonate, talc, clay, anhydrous silica, silica sand, titanium oxide, carbon black, quicklime and the like. These may be blended alone or in combination. The amount of the urethane prepolymer 10
0 to 500% by weight can be added to 0% by weight, preferably 0 to 400% by weight, more preferably 0 to 350% by weight.
% By weight. At this time, if the amount exceeds 500% by weight, sufficient strength tends not to be obtained, which is not preferable.

As a plasticizer, dioctyl phthalate,
General plasticizers such as dibutyl phthalate, dinonyl phthalate and dioctyl adipate can be used. These may be blended alone or in combination. It is added for the purpose of adjusting the viscosity, and the amount to be added is not particularly limited.

As the solvent, a conventional urethane solvent such as toluene, xylene, ethyl acetate, butyl acetate and terpene can be used. This is added for the purpose of adjusting the viscosity, and is added in an amount of about 1 to 10% of the whole composition. However, considering the effect on the working environment in addition to being a dangerous substance, the amount of addition is preferably 5% or less.

Examples of the additives include general organic moisture curing catalysts such as metal urethanization catalysts such as dibutyltin dilaurate and lead octylate, and tertiary amines such as triethylamine and N, N- (dimethylaminoethyl) morpholine. catalyst,
Antioxidants such as hindered phenols, ultraviolet absorbers such as benzotriazoles, etc. are used for the purpose of further improving curability, stability, weather resistance, and γ-aminopropyltrimethoxysilane, γ-glycidoxypropyl. A silane coupling agent such as trimethoxysilane and γ-mercaptopropyltrimethoxysilane can be added to the moisture-curable urethane resin in an amount of about 0.1 to 5% for the purpose of imparting adhesion to inorganic substances.

As the coloring agent, those which are usually used may be used, and pigments and dyes which produce a desired color may be appropriately used.

The moisture-curable sealing agent composition containing the moisture-curable urethane resin composition of the present invention as a main component is defined as a moisture-curable urethane resin having an extender pigment, an antisettling agent, a plasticizer,
It is obtained by appropriately mixing a solvent, an additive, a colorant, and the like, and kneading them using a high-viscosity stirrer such as a planetary mixer.

Examples of the extender used here include calcium carbonate, talc, clay, anhydrous silica, silica sand, titanium oxide, carbon black, quick lime and the like. These may be blended alone or in combination. The amount of the urethane prepolymer 10
0 to 500% by weight can be added to 0% by weight, preferably 0 to 400% by weight, more preferably 0 to 350% by weight.
% By weight. At this time, if the amount exceeds 500% by weight, sufficient strength tends not to be obtained, which is not preferable. Further, the anhydrous silica used here also acts as an anti-settling agent.

As the plasticizer, dioctyl phthalate,
General plasticizers such as dibutyl phthalate, dinonyl phthalate and dioctyl adipate can be used. These may be blended alone or in combination. The amount to be blended is not particularly limited.

As the solvent, a conventional urethane solvent such as toluene, xylene, ethyl acetate, butyl acetate, and terpene can be used. This is added for the purpose of adjusting the viscosity, and is added in an amount of about 1 to 20% of the whole composition. However, considering the hazardous materials regulations and the effect on the working environment, and considering the thinning of the solvent due to the volatilization of the solvent, the added amount is 5%.
The following is desirable.

The additives include metal catalysts such as dibutyltin dilaurate and lead octylate, triethylamine,
3 such as N, N- (dimethylaminoethyl) morpholine
General moisture curing catalysts such as secondary amines, antioxidants such as hindered phenols, ultraviolet absorbers such as benzotriazoles, etc. are used for the purpose of further improving curability, stability and weather resistance. About 0.1 to 3% can be added to each resin.

The moisture-curable urethane resin composition of the present invention is mainly composed of a moisture-curable urethane resin and a moisture-curable urethane resin, which is optionally blended with an extender, a thickener, an additive, and the like. These are paint shakers, 3
It is obtained by kneading using a pigment dispersion production device for paints such as this roll.

The extender used here includes calcium carbonate, talc, clay, anhydrous silica, silica sand, titanium oxide, carbon black, quick lime and the like. These may be blended alone or in combination. The amount of the urethane prepolymer 10
0 to 300% by weight can be added to 0% by weight, preferably 0 to 200% by weight, more preferably 0 to 150% by weight.
% By weight. At this time, if the compounding amount exceeds 300% by weight, sufficient coating film strength and adhesiveness tend not to be obtained, which is not preferable.

As the solvent, there can be used ordinary urethane solvents such as toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone and terpene. This is added for the purpose of adjusting the viscosity in consideration of spray coating, brush coating properties, and the like, and is added in the same amount as the composition. However, in consideration of the regulation of dangerous substances and the effect on the working environment, the amount of addition is desirably as small as possible within a range where workability can be maintained.

As additives, metal catalysts such as dibutyltin dilaurate and lead octylate, triethylamine,
3 such as N, N- (dimethylaminoethyl) morpholine
General moisture curing catalysts such as secondary amines, antioxidants such as hindered phenols, ultraviolet absorbers such as benzotriazoles, etc. are used for the purpose of further improving curability, stability and weather resistance. About 0.1 to 5% can be added to each resin. In addition, a general pigment dispersant for a solvent-based paint may be used.

As the colorant, those usually used may be used, and pigments and dyes which produce a desired color may be used as appropriate. Specifically, titanium oxide is generally used for white, and carbon black or the like is generally used for black.

[0030]

EXAMPLES Next, the present invention will be described more specifically with reference to Production Examples, Examples and Comparative Examples, but the present invention is not limited to these.

[Production Example] Production Example 1 (urethane prepolymer for NBDI-based building adhesive) A polyoxypropylene diol Diol-3000 having a molecular weight of 3000 (trade name; manufactured by Mitsui Toatsu Chemicals, Inc.) is placed in a reaction vessel capable of reducing pressure and stirring. ) 852 parts, molecular weight 500
0 polyoxypropylene triol MN-5000
(Product name: Mitsui Toatsu Chemicals, Inc.) 365 parts, 2,5
And / or 2,6-diisocyanatomethylbicyclo [2,2,1] heptane (hereinafter abbreviated as NBDI) (manufactured by Mitsui Toatsu Chemicals, Inc.) (284 parts), dibutyltin dilaurate (trade name: Neostan U-100; Nitto) Chemical product)
0.08 parts were weighed. The temperature was raised to 80 ° C. by using an oil bath while monitoring the heat generation, by passing dry nitrogen or stirring under reduced pressure so that moisture in the atmosphere was not mixed. After stirring was continued for 5 hours, the content was cooled to 40 ° C. or lower, and the contents were taken out. The resulting reaction product provided a urethane prepolymer having a viscosity of 6500 cps and an active isocyanate content of 5.5%.

Production Example 2 (Urethane prepolymer for MDI-based building adhesive) A reaction vessel similar to that used in Production Example 1 was charged with a molecular weight of 30.
00 polyoxypropylene diol Diol-30
00, 812 parts, polyoxypropylene triol MN-5000 having a molecular weight of 5000, 348 parts, 4,4′-
Diphenylmethane diisocyanate (trade name: MDI-
PH: 340 parts (manufactured by Mitsui Toatsu Chemicals, Inc.) and 0.05 part of dibutyltin dilaurate were charged and reacted under the same conditions as in Production Example 1 for 3 hours. The resulting reaction product has a viscosity of 820
A urethane prepolymer having 0 cps and an active isocyanate content of 5.5% was obtained.

Production Example 3 (Urethane prepolymer for IPDI (isophorone diisocyanate) -based building adhesive) A reaction vessel similar to that used in Production Example 1 was charged with a molecular weight of 30.
00 polyoxypropylene diol Diol-30
837 parts of OO, 359 parts of polyoxypropylene triol MN-5000 having a molecular weight of 5,000, 304 parts of isophorone diisocyanate (hereinafter abbreviated as IPDI) (manufactured by Huls), and 0.08 part of dibutyltin dilaurate. The reaction was performed for 6 hours under the same conditions. The resulting reaction product provided a urethane prepolymer having a viscosity of 6300 cps and an active isocyanate content of 5.5%.

Production Example 4 (Prepolymer for NBDI Sealer) Polyoxypropyldiol Di having a molecular weight of about 2000
ol-2000 (trade name; manufactured by Mitsui Toatsu Chemicals, Inc.) 5
12 parts and 354.3 parts of polyoxypropylene triol MN-3050 (trade name; manufactured by Mitsui Toatsu Chemicals, Inc.) having a molecular weight of about 3000 were placed in a reaction vessel, and 80 ° C., 10 m
Dehydration was performed for 120 minutes under reduced pressure of not more than mHg, and it was confirmed that the water content was not more than 0.05%. Then, 133.8 parts of NBDI was added as an organic isocyanate component, and 80 ° C.
The reaction was performed for 5 hours in a stream of dry nitrogen. Thereafter, 0.1 part of dibutyltin dilaurate was further added and reacted for 2 hours. After cooling, the obtained active isocyanate-containing urethane prepolymer had a viscosity of 46000 cps and an active isocyanate content of 1.8%.

Production Example 5 (Prepolymer for TDI Sealer) Polyoxypropyldiol Di having a molecular weight of about 2,000
ol-2000, and 436.1 parts of polyoxypropylene triol MN-3050 having a molecular weight of about 3000.
Production Example 4 except that 68.5 parts and 2,4 and / or 2,6-tolylene diisocyanate cosmonate T80 (trade name; manufactured by Mitsui Toatsu Chemicals, Inc.) 171.7 parts were used.
The same operation as described above was performed. As a result, the viscosity was 41500 cp.
s, a urethane prepolymer having an active isocyanate content of 1.8% was obtained.

Production Example 6 (Prepolymer for IPDI Sealer) Polyoxypropyldiol Di having a molecular weight of about 2,000
507 parts of polyoxypropylene triol MN-3050 having a molecular weight of about 3000
And the same operation as in Production Example 4 except that 142.8 parts of isophorone diisocyanate was used. as a result,
Viscosity 51500 cps, active isocyanate content 1.
8% urethane prepolymer was obtained.

Production Example 7 (NBDI prepolymer for paint) Polyester triol P-301 having a molecular weight of 3000
818 parts (trade name; manufactured by Kuraray Co., Ltd.) was placed in a reaction vessel, and dehydrated at 80 ° C. under a reduced pressure of 10 mmHg or less for 120 minutes to confirm that the water content was 0.05% or less. As an ingredient, NBDI 182
Then, the mixture was reacted at 80 ° C. in a dry nitrogen stream for 3 hours. Thereafter, 0.3 parts of dibutyltin dilaurate was further added and reacted for 2 hours. After cooling, the obtained active isocyanate-containing urethane prepolymer has a viscosity of 55000 c.
ps, the active isocyanate content was 4.0.

Production Example 8 (Comparative TDI prepolymer) As an organic isocyanate component, 844 parts of polyester triol P-3010 (trade name; manufactured by Kuraray Co., Ltd.) having a molecular weight of 3000 and 2,4 and / or 2,6-tolylenediene Except for using 156 parts of Isocyanate Cosmonate T80 (trade name; manufactured by Mitsui Toatsu Chemicals, Inc.), the same operation was performed using the same raw materials as in Production Example 6. as a result,
Viscosity 43000 cps, active isocyanate content 4.
0% urethane prepolymer was obtained.

Production Example 9 (Comparative IPDI non-yellowing prepolymer) As an organic isocyanate component, 818 parts of polyester triol P-3010 having a molecular weight of 3000 (trade name, manufactured by Kuraray Co., Ltd.) and isophorone diisocyanate 19
Except for using 5 parts, the same operation was performed using the same raw materials as in Production Example 6. As a result, a urethane prepolymer having a viscosity of 49000 cps and an active isocyanate content of 4.0% was obtained.

Example 1 Example 1 (Urethane adhesive composition for NBDI-based building adhesive) 100 parts of the urethane prepolymer of Production Example 1 was mixed with calcium carbonate (trade name: T heavy coal; Maruo Calcium Co., Ltd.)
150 parts), 45 parts of DOP (dioctyl phthalate: manufactured by Kyowa Hakko Co., Ltd.) and 10 parts of anhydrous silica (trade name: Aerosil # 200; manufactured by Nippon Unicar Co., Ltd.) were mixed with a high viscosity material such as a planetary mixer. The mixture was charged into an apparatus capable of mixing and kneading, and kneaded under reduced pressure at 40 ° C. for 30 minutes. Next, 1 part of an aminosilane coupling agent was added, and after kneading for 15 minutes, 1 part of a glycidylsilane coupling agent and 0.1 part of dibutyltin dilaurate were further charged and stirred for 15 minutes. Finally, the pressure in the kettle was reduced to 100 mmHg or less for defoaming, kneading was performed for 30 minutes, and the mixture was taken out into a sealed container such as an aluminum pack that shuts out outside air. Thus, a one-part moisture-curable urethane adhesive composition of the present invention was obtained.

Example 2 (NBDI-based sealing composition) In a 3 liter planetary mixer, 200 parts of dioctyl phthalate, calcium carbonate dried at 150 ° C to a water content of 0.1% or less (trade name: Super SSS; Maruo) 600 parts of Calcium Co., Ltd., 50 parts of titanium oxide (trade name: CR-90, manufactured by Taipaque Co.), 10 parts of weather stabilizer (trade name: Irganox 1010, manufactured by Ciba Geigy Co., Ltd.) at 100 ° C. The temperature was increased while kneading. Then, a dehydration operation was performed in vacuum for 60 minutes while kneading. Next, 700 parts of the isocyanate-containing prepolymer synthesized in Production Example 4 and dibutyltin dilaurate 1.4
Part, anti-settling agent (hydrophobic silica R-972 (trade name),
Nippon Aerosil Co., Ltd.) 15 parts, toluene 150
The mixture was kneaded at room temperature for 10 minutes and then further reduced in pressure and kneaded for 10 minutes. Thus, a one-part moisture-curable urethane sealing composition of the present invention was obtained.

Example 3 (NBDI-based paint composition) 150 parts of titanium oxide (white) (PWC) obtained by drying the urethane prepolymer obtained in Production Example 7 at 150 ° C. to a water content of 0.1% or less at 150 ° C. = 50%) and a thinner for dilution (ethyl acetate / toluene / methyl ethyl ketone = 2)
/ 1/1), 50 parts of dibutyltin dilaurate 0.3
Part of the glass beads having a particle diameter of about 2 mm.
0 parts were added. The mixture was dispersed in a special container with a paint shaker for 2 hours. The glass beads were separated by filtration to obtain a one-pack type moisture-curable coating composition of the present invention. (Note) PWC (= Pigment Weight Co
nent): The proportion of the pigment in the paint solids.

Comparative Example 1 (Urethane adhesive composition for MDI-based building adhesive) Except for using the urethane prepolymer of Production Example 2, the same operation was carried out in the same blending ratio as in Example 1 to obtain a one-component moisture. A curable urethane adhesive composition was obtained.

Comparative Example 2 (Urethane adhesive composition for IPDI-based building adhesive) Except for using the urethane prepolymer of Production Example 3, the same operation was carried out at the same compounding ratio as in Example 1 to obtain a one-part moisture. A curable urethane adhesive composition was obtained.

Comparative Example 3 (TDI-based sealing composition) A one-pack type moisture-curable urethane sealing composition was prepared in the same manner as in Example 2 except that the urethane prepolymer of Production Example 5 was used. I got

Comparative Example 4 (IPDI-based sealing composition) A one-pack type moisture-curable urethane sealing composition was prepared in the same manner as in Example 2 except that the urethane prepolymer of Production Example 6 was used. I got

Comparative Example 5 (TDI coating composition) A one-pack type moisture-curable coating composition was prepared in the same manner as in Example 3 except that the urethane prepolymer of Production Example 8 was used. I got

Comparative Example 6 (IPDI-based coating composition) A one-pack type moisture-curable coating composition was prepared in the same manner as in Example 3 except that the urethane prepolymer of Production Example 9 was used. I got

[Evaluation Method] Adhesive Performance Test Using the compositions prepared in Example 1 and Comparative Examples 1 and 2, an exterior tile (trade name: Harukayan (semi-brick size: 45 mm × 145 mm); INAX ( Co., Ltd.) and a ceramic siding board (trade name: Honban; manufactured by Asahi Glass Co., Ltd.). First, 5mm of adhesive
It was spread with a comb-shaped iron having a width, the tiles were adhered, and left in an atmosphere of 20 ° C. and a relative humidity of 65%. In addition, apply only the adhesive in a 1 mm thick sheet and spread it at 20 ° C and 65% relative humidity.
After standing for 7 days in an atmosphere, an accelerated weather resistance test (irradiation for 200 hours with a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.)) was performed. Table 1 shows the results.

[0050]

[Table 1]

As can be seen from the results, Comparative Example 1 was yellowed and the appearance was deteriorated, and Comparative Example 2 was good in weather resistance, but slow in reaction with moisture and insufficient in initial curing. In contrast, it was found that the composition of Example 1 had excellent weather resistance and good moisture curability.

Sealing performance test The compositions prepared in Example 2 and Comparative Examples 3 and 4 were measured for tack free time according to JIS-A 5758 (1986) for curability and mechanical properties were measured according to JIS-K6301. It measured by the method according to. An accelerated weathering test (200 hours) was also performed as described above. Table 2 shows the results.

[0053]

[Table 2]

As can be seen from the results, Comparative Example 3 was yellowed and the appearance was deteriorated, and Comparative Example 4 was good in weather resistance but slow in reacting with moisture and insufficient in initial curing. In contrast, the composition of Example 2 was found to be excellent in weather resistance and moisture curability. As can be seen from the results, it was found that the composition of Example 2 had excellent weather resistance and good moisture curability.

Paint Performance Test The compositions prepared in Example 3 and Comparative Examples 5 and 6 were applied to a mild steel plate (trade name: Bonderite # 1077) degreased with isopropyl alcohol to a thickness of 30 microns.
After pre-drying at 50 ° C for 20 minutes, 20 ° C and relative humidity 65%
Was allowed to stand for one week in a constant temperature / humidity chamber, and the reaction with moisture was allowed to proceed to form a paint film. Using this, JIS-K 5400
The evaluation was performed according to. Accelerated weathering test (500 hours)
Was also performed. Table 3 shows the results.

[0056]

[Table 3]

As can be seen from the results, Comparative Example 5 was yellowed and the appearance was deteriorated, and Comparative Example 6 had good weather resistance, but had a slow reaction with moisture and was insufficient in initial curing. In contrast, the composition of Example 3 was found to be excellent in weather resistance and moisture curability.

[0058]

As is apparent from the above results, at least 2,5 and / or 2,6-diisocyanatomethylbicyclo [2,2,
1] A moisture-curable urethane resin composition of the present invention comprising a urethane prepolymer composition obtained by reacting a heptane-containing organic isocyanate with an active hydrogen compound having at least one active hydrogen group in a molecule Is characterized by having excellent weather resistance, good reactivity with moisture, and excellent initial curability. Furthermore, by using the moisture-curable urethane resin composition of the present invention, a building adhesive composition having excellent weather resistance, good reactivity with moisture, and excellent initial curing properties, and a sealing agent are provided. Compositions, coating compositions can be provided.

Continuation of the front page (51) Int.Cl. ⁶ Identification code FI C09K 3/10 C09K 3/10 D (72) Inventor Kosuke Suewaka 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Mitsui Chemicals, Inc.

Claims (9)

[Claims] 1. A moisture-curable urethane resin composition comprising a urethane prepolymer having an active isocyanate group capable of reacting with moisture in the air, wherein the organic isocyanate having an active isocyanate group contains at least 2,5.
And / or 2,6-diisocyanatomethylbicyclo [2,2,1] heptane. A moisture-curable urethane resin composition. 2. The content of 2,5 and / or 2,6-diisocyanatomethylbicyclo [2,2,1] heptane in all organic isocyanates used in the urethane prepolymer is 20 to 100% by weight. The moisture-curable urethane resin composition according to claim 1, wherein: 3. The urethane prepolymer contains 2 per molecule.
The organic isocyanate containing at least one isocyanate group and an active hydrogen compound having at least one active hydrogen group in one molecule are obtained by reacting the compound with each other. A moisture-curable urethane resin composition. 4. The ratio (A / B) of the number (A) of the isocyanate groups of the organic isocyanate to the number (B) of the active hydrogen groups of the active hydrogen compound is from 1.2 to 10. The moisture-curable urethane resin composition according to claim 3. 5. A moisture-curable urethane resin composition, wherein a urethane-forming catalyst is used in producing the urethane prepolymer according to claim 3. 6. The reaction temperature for producing the urethane prepolymer according to claim 3 is 30 to 12.
A moisture-curable urethane resin composition, which is at 0 ° C. 7. A moisture-curable adhesive composition comprising the moisture-curable urethane resin composition according to claim 1 as a main component. 8. A moisture-curable sealant composition comprising the moisture-curable urethane resin composition according to claim 1 as a main component. 9. A composition for a moisture-curable coating composition comprising the moisture-curable urethane resin composition according to claim 1 as a main component.