JPH09194560A - Moisture-setting composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition containing a modified polyisocyanate produced by reacting a polyol with a polyisocyanate, useful as a coating material, an adhesive, etc., especially a coating material for heavy anticorrosion and excellent in durability and weather resistance. SOLUTION: This moisture-setting composition contains (C) a modified polyisocyanate produced by reacting (A) at least one kind of a polyol selected from a polycarbonate polyol, an acrylic polyol and a silicone polyol with (B) a polyisocyanate. The average value of remained isocyanate groups of the component C per every molecule of the resultant product is preferably 2.2-3.0. Further, the content of the component C is preferably 20-80wt.% of the total of the composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a moisture-curable composition applicable to paints, adhesives, sealants, etc., and particularly to a moisture-curable composition excellent in durability and weather resistance and suitable for heavy-duty anticorrosion paint applications. Regarding things.

[0002]

2. Description of the Related Art Conventionally, polyurethane resin has a rubber elasticity.
It has been used for paints, sealants, flooring agents, wall agents, waterproofing agents or adhesives because of its excellent wear resistance, durability, weather resistance and adhesion to base materials. These polyurethane resins are known as one-pack type and two-pack type. Among these, the moisture-curable polyurethane resin consisting of an organic isocyanate compound, which is a one-component urethane resin, does not have the trouble of mixing two-components at the execution site like the two-component type such as acrylic-urethane type, and is in the air. Since it reacts and cures quickly with the moisture of, it is widely used for paints, sealants, flooring materials, wall materials, waterproofing agents and adhesives.

So far, one-component type moisture-curable urethane resins synthesized from various polyols and polyisocyanates have been proposed. As these polyols, low molecular weight polyols, polyether polyols, polyester polyols, etc. have been used. In particular, the aliphatic polyester polyol has been used mainly as a resin component for a top coating because it has excellent pigment dispersibility, initial gloss, and weather resistance as compared with a polyether type. However, the moisture-curable urethane resin using the aliphatic polyester polyol has a problem that the water resistance is poor and the long-term weather resistance is insufficient.

[0004]

Therefore, the present inventors have found that the conventional moisture-curable urethane resin has water resistance, durability, and
Provided is a moisture-curable composition having improved weather resistance, which is applicable to paints, adhesives, sealants, etc., particularly, a moisture-curable composition having excellent durability and weather resistance suitable for heavy anticorrosion paint applications. To aim.

[0005]

In order to achieve the above object, the inventors of the present invention, in order to achieve the above object, have a polycarbonate, an acrylic polyol and / or a silicone polyol, which are polyols excellent in weather resistance, light resistance and water resistance, and a poly. By reacting an isocyanate compound to synthesize a modified polyisocyanate having a high weather resistance component as a main structure, the modified polyisocyanate alone or coexisting with an aliphatic polyester polyol modified polyisocyanate obtained from a conventional aliphatic polyester polyol is used. It has been found that a moisture-curable composition as a main component can provide a coating film / sealant / adhesive layer having excellent weather resistance, light resistance and water resistance, and has reached the present invention.

That is, the present invention is characterized by containing a modified polyisocyanate obtained by reacting at least one polyol selected from polycarbonate polyol, acrylic polyol, and silicone polyol as polyisocyanate. It is a composition.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Polycarbonate polyols, acrylic polyols, and silicone polyols are used as polyols for synthesizing the modified polyisocyanate of the moisture-curable composition of the present invention.

As the polycarbonate polyol used in the present invention, a polyol having a structure represented by the following general formula (1) is preferably used.

[0009]

Embedded image Here, in the formula, X is a hydrocarbon group, n is a natural number, R
¹ is a methylene group, an ethylene group, a linear alkylene group such as n-propylene group, an isopropylene group, a sec-butylene group, a branched alkylene group such as tert-butylene, 1,1
-Cyclohexylene group, 1,2-cyclohexylene group,
Alicyclic hydrocarbon group such as 1,3-cyclohexylene group or 1,4-cyclohexylene group, arylene group such as phenylene group and naphthylene group, oxymethylene group, ether such as oxypropylene group A group, a bisphenol-type skeleton such as bisphenol A, bisphenol F, bisphenol S, or the like is shown, and each may show a repeating structure of one or more times. R ¹ may be substituted with various substituents such as a halogeno group such as fluorine, chlorine and bromine, a cyano group, a carboxyl group, a sulfonic acid group, a nitro group, a hydroxy group and an alkoxy group. . Further, R ¹ is an unsaturated group such as a vinylene group, a carbonyl group, a carboxyl group, an ether group,
There is no problem even if one or more thioether groups, urethane groups, urea groups, thiourea groups, etc. are contained at the terminals, both terminals, inside or in the repeating unit. Also,
R ¹ may be the same or different. Among them, as the polycarbonate polyol excellent in weather resistance, particularly yellowing resistance, an aliphatic polycarbonate polyol which is a linear alkylene group is more preferably used. Further, when the moisture-curable resin of the present invention is used as an overcoating material, the molecular weight of the aliphatic polycarbonate polyol is preferably 300 to 2000, from the viewpoints of flexibility, coatability, amorphousness, transparency and high gloss retention. , And more preferably from 500 to 1500 is used.

The type of the acrylic polyol used in the present invention is not particularly limited, but acrylic diol is preferably used. Specific examples of such an acrylic diol include the following general formula (2) or (when polymerizing various acrylic acid-based monomers, for example, acrylic acid esters such as methyl methacrylate, propyl methacrylate, and isobutyl methacrylate. Acrylic diol modified at both ends with OH groups obtained by using a hydroxyl group-containing initiator / terminating agent such as the compound represented by 3) and / or a chain transfer agent is preferably used.

[0011]

Embedded image

Embedded image However, in the formula, R ² , R ³ , R ⁶ and R ⁷ are linear alkylene groups such as methylene group, ethylene group and n-propylene group, isopropylene group, sec-butylene group, tert-butylene and other branched groups. Alicyclic hydrocarbon group such as linear alkylene group, 1,1-cyclohexylene group, 1,2-cyclohexylene group, 1,3-cyclohexylene group or 1,4-cyclohexylene group, phenylene Group, allylene group such as naphthylene group, ether group such as oxymethylene group, oxypropylene group, one or more repeating structures such as bisphenol type skeleton such as bisphenol A, bisphenol F, bisphenol S, and further fluorine, chlorine, bromine Substituted with various substituents such as halogeno group, cyano group, carboxyl group, sulfonic acid group, nitro group, hydroxy group, alkoxy group, etc. It may be one,
Unsaturated group such as vinylene group, carbonyl group, carboxyl group, ether group, thioether group, urethane group, urea group, thiourea group, etc. may be contained at one or more in the terminal, both terminals, internal or repeating unit. No problem. Further, these R ² , R ³ , R ⁶ and R ⁷ are
They may be the same or different. Further, in the formula, R ⁴ and R ⁵ are each a linear alkyl group such as a methyl group, an ethyl group, and an n-propyl group, an isopropyl group, a sec-butyl group, a branched alkyl group such as tert-butyl, a cyclohexyl group. Alicyclic hydrocarbon group such as a group,
Phenyl group, allyl group such as naphthyl group, methoxy group,
Ethoxy, alkoxy groups such as phenoxy group or phenoxy group, benzyl group, aralkyl groups such as phenethyl group, halogen groups such as fluorine, chlorine, bromine, cyano group, further these are halogen group, cyano group, carboxyl group, Sulfonic acid group, nitro group, hydroxy group,
It may be substituted with various substituents such as an alkoxy group. Further, R ⁴ and R ⁵ may be an unsaturated group such as a vinylene group, a carbonyl group, a carboxyl group, an ether group, a thioether group, a urethane group, a urea group, a thiourea group, etc., one or more in an internal unit or a repeating unit. It does not matter at all if it is included. R ⁴ and R ⁵ may be the same or different. The hydroxyl group-containing initiator / terminating agent and / or the chain transfer agent may be used alone or as a mixture of two or more kinds.

As the silicone polyol used in the present invention, a silicone oil whose main chain has a repeating structure of Si--O bonds, or a polyether resin or alcohol-modified silicone resin is preferably used. The substituent of the Si atom in the main chain is not particularly limited, but is usually a methyl group, an alkyl group such as an ethyl group or a halogeno group such as fluorine, chlorine or bromine, a cyano group, a carboxyl group, or a sulfone. Those substituted with various substituents such as acid groups, nitro groups, hydroxy groups, and alkoxy groups are used, but the stability of the bond between the Si atom and the substituents, the stability of the silicone polyol-modified polyisocyanate, the moisture curability An alkyl group such as a methyl group or an ethyl group is more preferably used in view of various properties such as stability of the composition, durability of paints, sealants, flooring agents, wall agents, waterproofing agents, adhesives and the like, and weather resistance. In addition, one or more unsaturated groups such as vinylene group in the main chain, carbonyl group, carboxyl group, ether group, thioether group, urethane group, urea group, thiourea group, etc. at the end, both ends, internal or repeating unit. It does not matter at all if you include them.

The molecular weight of these polyols used in the present invention is 200 to 10,000, preferably 30.
0-5000, more preferably 300-3000 polyols are used. These polyols may be used not only alone but also as a mixture of two or more kinds.

The modified isocyanate of the moisture curable composition of the present invention is synthesized from the above polyol and polyisocyanate. Examples of the polyisocyanate used in these syntheses include trimethylene diisocyanate,
Tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,
2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate,
1,3-butylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-
Trimethylhexamethylene diisocyanate, 2,6-
Aliphatic diisocyanates such as diisocyanate methylcaproate, 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3
-Cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4 ^, -methylenebis (cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1 , 4-bis (isocyanatomethyl)
Cycloalkylene, cycloalkylene-based diisocyanates such as 1,3-bis (isocyanatomethyl) cyclohexane, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4 ^, -diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,
4 ^, -diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate and 2,6-
Mixtures of tolylene diisocyanate, ^4,4, - toluidine diisocyanate, ^4,4, - toluidine diisocyanate, dianisidine diisocyanate, ^4,4, -
Aromatic diisocyanates such as diphenyl ether diisocyanate, 1,3-xylylene diisocyanate,
1,4-xylylene diisocyanate, a mixture of 1,3-xylylene diisocyanate and 1,4-xylylene diisocyanate, ω, ω ^, -diisocyanate-1,4
-Aroaliphatic diisocyanates such as dimethylbenzene, 1,3- or 1,4-bis (α, α-dimethylisocyanatomethyl) benzene, triphenylmethane-
^4,4, 4 ^,, - triisocyanate, 1,3,5-triisocyanate benzene, 2,4,6-triisocyanate toluene triisocyanate, ^4,4, - diphenyl dimethyl methane ^2,2,, 5, Tetraisocyanate such as 5 ^, -tetraisocyanate is preferably used. Further, polymerized polyisocyanates composed of the above-mentioned isocyanate compounds such as dimers of tolylene diisocyanate converted to trimers, and polyisocyanates such as polyphenyl polymethylene polyisocyanate are also preferably used. Further, these compounds can be used not only alone but also as a mixture of two or more kinds.

In the moisture-curable composition of the present invention, if there are too many residual isocyanate groups per molecule of modified polyisocyanate, the stability during storage tends to deteriorate.
On the other hand, if the amount is too small, the coating film or the like tends to be poorly cured and / or poor in durability, so that the residual isocyanate group is preferably 2.2 to 3.0, more preferably 2.3 to 2. 9, more preferably 2.4-2.
8

In the moisture-curable composition of the present invention, the content of the modified polyisocyanate is not particularly limited, but is preferably 20 to 20% of the whole moisture-curable composition.
80% by weight, more preferably 30-70% by weight of the total moisture-curable composition.

If necessary, a polyether polyol, a polyester polyol, a polyether ester polyol, a polybutadiene polyol, a polyisoprene polyol, etc. may be added to the polyol used for synthesizing the modified polyisocyanate of the moisture-curable composition of the present invention. You can

Examples of such polyether polyols include ethylene oxide, propylene oxide, a mixture of ethylene oxide and propylene oxide, and a ring-opening polymer of tetrahydrofuran obtained by using ethylene glycol, propylene glycol, glycerin, pentaerythritol and the like as an initiator. Can be mentioned.

Further, as the polyester polyol,
2 or 3 basic acids such as maleic acid, fumaric acid, succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, isophthalic acid, terephthalic acid and trimellitic acid, and 2
˜Condensation products with tetrahydric polyhydric alcohols are mentioned. Specific examples of such polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,
5-pentene glycol, 1,6-butylene glycol, neopentyl glycol, decamethylene glycol, 2,4,4-trimethyl-1,3-pentane glycol, cyclohexanediol, cyclohexanemethanol, xylylene glycol, hydroquinone bis (hydroxyethyl) Ether), hydrogenated bisphenol A, trimethylolpropane, glycerin, 1,2,6-hexanetriol, pentaerythritol, castor oil and the like. Further, higher fatty acids, for example, coconut oil fatty acid, linseed oil fatty acid, soybean oil fatty acid, cottonseed oil fatty acid, millet oil fatty acid, dimer acid, hydrogenated dimer acid and castor oil fatty acid are blended in the acid component, and oil modified A polyester polyol can be used.

Further, as the polyether ester polyol, one obtained by reacting the above polyether polyol with a polybasic acid to form a polyester or one having both polyether and polyester segments in the molecule,
For example, a polyol obtained by ring-opening copolymerization of an epoxy compound and an acid anhydride may be mentioned.

In the moisture-curable composition of the present invention, various additives may be added, if necessary, in order to sufficiently cure the moisture-curable composition. Further, it is also preferably added for the purpose of improving the curing degree of the moisture-curable composition and maintaining / improving various physical properties such as a cured coating film / sealant / adhesive layer, particularly durability and weather resistance. Examples of such additives include a curing catalyst, a solvent, a surfactant, a stabilizer, a weather resistance improver, a light resistance improver, and an antioxidant.

Examples of the curing catalyst preferably added to the moisture-curable composition of the present invention include tertiary amines and metal catalysts.

Specific examples of such a tertiary amine include:
For example, triethylenediamine, ^{N, N, N,, N,,}
N ^,, -pentamethyldipropylenetriamine, N, N,
^{N,, N,,} N ^,, - pentamethyldiethylenetriamine, N, ^N, N,, ^N, - tetramethylhexamethylenediamine, bis (dimethylamino) ether, 2
-(N, N ^, -dimethylamino) ethyl-3- (N, N
^, -Dimethylamino) propyl ether, N, N ^, -dimethylcyclohexylamine, N, N ^, -dicyclohexylmethylamine, methylenebis (dimethylhexyl)
Amine, N, ^N, dimethyl cetyl amine, N, ^N, - dimethyl dodecylamine, N, ^N, - dimethyl ^{hexadecylamine, N, N, N,,} N, - tetramethyl-1,3
-Butanediamine, N, N ^, -dimethylbenzylamine, morpholine, N-methylmorpholine, N-ethylmorpholine, N- (2-dimethylamino) morpholine,
4,4 ^, -oxydiethylenedimorpholine, N, N ^, -
Diethyl piperazine, N, N ^, -dimethyl piperazine,
N-methyl-N ^, -dimethylpiperazine, 2,4,6-
Tri (dimethylaminomethyl) phenol, tetramethyl Harrow di Nin, 3-dimethylamino -N, ^N, - dimethyl propionamide, N, ^N, N,, ^N, - tetra
(3-Dimethylaminopropyl) methanediamine, N,
^N, - dimethylaminoethanol, ethoxylated hydroxylamine, N, ^N, N,, ^N, - tetramethyl-1,
3-diamino-2-propanol, N, N, N ^, -trimethylaminoethanolamine, 1,4-bis (2-hydroxypropyl) 2-piperazine, 1- (2-hydroxypropyl) imidazole, 3,3-diamino -N-
Methyl dipropylamine, 1,8-diazabicyclo [5.4.0] - undecene -7, N-methyl ^-N,,
-Hydroxyethylpiperazine and the like. Among these, preferably, bis (dimethylaminomethyl) ether, 2- (N, N-dimethylamino) propyl ether, triethylamine, N- (2-dimethylaminoethyl) morpholine, 3-dimethylamino-N, N-dimethyl. Propionamide and N, N-dimethylaminoethanol are used, and more preferably triethylenediamine is used. In addition, these tertiary amines are used individually or as a mixture of 2 or more types.

The amount of these tertiary amines added is 0.0 based on the resin solid content of the moisture-curable composition of the present invention.
A suitable amount is 5 to 3% by weight, preferably 0.1 to 2% by weight. When the addition amount of the tertiary amine is 0.05% by weight or less,
Since the urethanization reaction of the polyol and the polyisocyanate is not completed sufficiently, a large amount of unreacted polyisocyanate remains in the composition, and the coating film / sealing material / adhesive layer obtained by the composition has poor curing and durability. It tends to cause defects. In particular, when the composition is used as a material for various top coats, it is not preferable because it becomes a main factor of lowering the gloss retention rate and yellowing and chromaticity change. Further, when the amount of addition of the tertiary amine is 3% by weight or more, in the urethane-forming reaction of the polyol and the polyisocyanate, the isocyanate groups in the reaction system excessively react to cause gelation, so that the moisture-curable composition of the present invention is used. Product yield tends to deteriorate. Further, when the curable composition of the present invention is used as various top coating materials, an excessive amount of tertiary amine causes yellowing /
It tends to cause a change in chromaticity, so caution is required.

A metal catalyst is preferably added to the moisture-curable composition of the present invention. Specific examples of such metal catalysts include, for example, bismuth nitrate, lead 2-ethylhexonate, lead benzoate, lead oleate, sodium trichlorophenolate, sodium propionate, lithium acetate, potassium oleate, tetrabutyltin, chloride. Tin, tributyltin cyanate, tin octylate, tin tartrate, dibutyltin di (2-ethylhexaate), dibutyltin dilaurate, dibutyltin diisooctyl maleate, dibutyltin dibutoxide, dibutyltin dibutoxide, dibutyltin bis (o- Phenylphenoate), dibutyltin bis (acetylacetonate), di (2-ethylhexyl) tin oxide, titanium tetrachloride, dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride, iron trichloride, iron 2-ethylhexonate (III), a Chiruaseton iron (III), ferrocene, antimony trichloride, antimony pentachloride, two triphenyl antimony chloride, triphenyl antimony, uranium nitrate, cadmium nitrate, diethyl dithiophosphoric acid cadmium, cobalt benzoate, 2-Echiruhekison cobalt, nitric thorium,
Triphenyl aluminum, aluminum oleate,
Diphenyl mercury, zinc 2-ethylhexonate, zinc naphthenate, nickelocene, hexacarbonyl molybdenum,
Cerium nitrate, vanadium trichloride, copper 2-ethylhexonate, copper acetate, manganese 2-ethylhexonate, zirconium 2-ethylhexonate, triphenylarsenic, arsenic trichloride, boron trifluoride-diethyl ether complex, pyridineborane, calcium acetate , Barium acetate and the like. Further, as the metal catalyst which is more preferably added to the moisture-curable composition of the present invention, an organic tin compound which exhibits a catalytic action in the reaction between an isocyanate group and a hydroxyl group can be mentioned. Specifically, for example, tetra-n-butyl-
1,3-diacetyloxydistannoxane, tetra-n
-Propyl-1,3-diacetyloxydistannoxane, tetra-n-propyl-1-chloro-3-diacetyloxydistannoxane, tetra-n-butyl-1-chloro-3-diacetyloxydistannoxane, tetra Methyl-1,3-diacetyloxydistannoxane, tetra-n-butyl-1,3-diacryloxydistannoxane, tetra-n-butyl-1,3-dioleyloxydistannoxane, tetra-n- Butyl-1,3-diformyloxydistannoxane, tetra-n-butyl-1,
3-distearyloxydistannoxane, tetra-n-
Butyl-1,3-diphenylacetyloxydistannoxane, tetra-n-butyl-1,3-diisocyanooxydistannoxane, tetra-n-butyl-1-acetyloxy-3-hydroxydistannoxane, tetra -N-
Propyl-1-acetyloxy-3-hydroxydistannoxane, tetra-n-propyl-1-acetyloxy-3-hydroxydistannoxane, tetramethyl-1-
Acetyloxy-3-hydroxydistannoxane, tetra-n-butyl-1,3-dichlorodistannoxane, tetramethyl-1,3-dichlorodistannoxane, tetra-n-butyl-1,3-dipropoxydista Noxane,
Tetra-n-propyl-1,3-dipropoxydistannoxane, tetra-n-butyl-1-propoxy-3-acetyloxydistannoxane, tetra-n-propyl-
1-hydroxy-3-ethoxyoxydistannoxane,
1,1-dibutyl-3,3-dipropyl-1-hydroxy-3-acetyloxydistannoxane, 1,3-dipropyl-1,3-dibutyl-1-chloro-3-hydroxydistannoxane and the like can be mentioned. . In addition, these metal catalysts are used individually or as a mixture of 2 or more types. More preferably, tin octylate, dibutyltin dilaurate, and organotin compounds such as distaquinosans are used.

The amount of the metal catalyst added is 0.001 to 5% by weight, preferably 0.01 to 1% by weight, more preferably 0.001 to 5% by weight, based on the resin solid content of the moisture-curable composition of the present invention. A suitable amount is 0.01 to 0.1% by weight. When the addition amount of the metal catalyst is 0.001% by weight or less, the urethanization reaction of the polyol and the polyisocyanate is not sufficiently completed, and a large amount of unreacted polyisocyanate remains in the composition, and the coating obtained by the composition is obtained. There is a tendency for poor curing and durability of the film, sealing material, and adhesive layer. In particular, when the composition is used as a material for various top coats, it is not preferable because it becomes a main factor of lowering the gloss retention rate and yellowing and chromaticity change. Also, the addition amount of the metal catalyst is 5% by weight.
In the above, in the urethanization reaction of the polyol and the polyisocyanate, the isocyanate group in the reaction system excessively reacts to cause gelation, so that the yield of the moisture-curable composition of the present invention tends to decrease. In addition, when the moisture-curable composition of the present invention is used as various top coats, an excessive amount of the metal catalyst tends to cause yellowing and change in chromaticity, so caution is required.

Further, the moisture-curable composition of the present invention is preferably an organic solvent in order to improve the fluidity / coating property and filling property of the composition, or the uniformity of the cured coating film / adhesive layer / sealant. Is added. By adding the organic solvent, coating, application of adhesive, filling of sealant, etc. can be facilitated. As such an organic solvent, in order to maintain the reactivity of the unreacted isocyanate group of the modified polyisocyanate which is the main component of the moisture-curable composition of the present invention, an organic solvent having no active hydrogen is preferable, for example, acetic acid. Preferred are esters such as ethyl, butyl acetate, cellosolve acetate, ketones such as acetone / methyl ethyl ketone / methyl isobutyl ketone, aromatic hydrocarbons such as benzene / toluene / xylene, and cyclic ethers such as tetrahydrofuran / dioxane / trioxane. Used. Among these organic solvents, acetone, cellosolve acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, tetrahydrofuran,
Dioxane and the like are more preferably used. In addition, these organic solvents can be used individually or in mixture of 2 or more types.

To the moisture-curable composition of the present invention, various ultraviolet absorbers and antioxidants are added to improve the weather resistance, light resistance and oxidation deterioration resistance of the cured coating film / sealant / adhesive layer. be able to. In addition, UV absorption, or
It is also possible to copolymerize a monomer having an antioxidant property.
Examples of these various UV absorbers and antioxidants include benzophenone-based UV absorbers, phenylbenzoate-based UV absorbers, and hindered amino group-based antioxidants. It is preferable to use these additives in the range of 0.5 to 20% by weight. If it is less than 0.5% by weight, the effect of addition is not observed, and if it exceeds 20% by weight, heat resistance, mechanical strength and the like tend to be lowered.

Further, various additives are added to the moisture-curable composition of the present invention and the paint, sealant, flooring agent, wall agent, waterproofing agent, adhesive, etc. containing the moisture-curable composition of the present invention as a main component. It is also possible to contain various improving agents. It is possible to add various surfactant additives for the purpose of improving the surface smoothness, specifically, silicon-based compounds,
Fluorinated surfactants, organic surfactants and the like can be used. It is also possible to improve various practical properties by using various epoxy resins, melamine resins, amide resins and the like. Further, various curing agents other than the above-mentioned tertiary amines and metal catalysts may be used in combination for the purpose of accelerating curing or curing at low temperature. Specific examples of these curing agents include various organic acids and their acid anhydrides, nitrogen-containing organic compounds, various metal complex compounds, metal alkoxides, and various organic carboxylates of alkali metals, carbonates and the like. Examples thereof include salts, and radical polymerization initiators such as peroxides and azobisisobutyronitrile. These curing agents can be used as a mixture of two or more kinds.

The coating composition containing the moisture-curable composition of the present invention as a main component is used for any of the top coat, intermediate coat and base coat,
In particular, it is preferably used as an overcoating material, more specifically, as a single-layer coating or a multi-layer coating of two or more layers. Further, the coating material containing the moisture-curable composition of the present invention as a main component can be easily used by a commonly used coating method such as brush coating, dip coating, roll coating, spray coating, spin coating and flow coating.

In applying the coating material containing the moisture-curable composition of the present invention as a main component, various pretreatments may be applied for the purpose of improving cleaning, adhesion, water resistance and the like. As the pretreatment for these purposes, a usual keren treatment is preferably used, but an activated gas treatment, a chemical treatment, an ultraviolet treatment and the like are also possible. These pretreatments can be carried out continuously or stepwise in combination. Further, these pretreatments can be carried out continuously or stepwise in combination.

[0032]

EXAMPLES The present invention will be described more specifically below based on examples.

Various characteristics were measured as follows.

(A) Gloss value According to JIS Z 8741 "Measurement method of specular glossiness", portable gloss meter GM manufactured by Nichisho Co., Ltd.
The specular gloss ratio was measured using X-202 and defined as the gloss ratio.

(B) Chromaticity / color difference L ^* a ^* specified in JIS Z 8809 "Color difference display method"
The chromaticity E = (L ^* , a ^* , b ^* ) of the b ^* coordinate system was defined as the chromaticity of the present invention. Further, the color difference of the present invention is the distance on the L ^* a ^* b ^* coordinate system, that is, ((L ² −L ¹ ) ² + (a ² −a ¹ ) ² +, for each chromaticity determined by the above standard. (B ² −
b ¹ ) ² ) ^1/2 , both manufactured by Suga Test Instruments Co., Ltd., S
It measured using the M computer.

(C) Solvent resistance and xylene rubbing resistance The surface was rubbed with gauze impregnated with xylene, and the change in gloss at that time was visually evaluated.

(D) Adhesiveness Based on the cross-cutting method and the cross-cutting tape method stipulated in JIS K 5400 "General Test Method for Paints", the presence or absence of peeling of the coating film was examined to determine the degree of adhesion.

Example 1 First, 250 g of isophorone diisocyanate, 0.25 g of dibutyltin dilaurate, 2.5 g of triethylenediamine and 250 g of xylene were mixed at room temperature to prepare a uniform solution (hereinafter referred to as solution (I)). . On the other hand, polycarbonate diol (manufactured by Daicel Chemical Industries, Ltd.,
Product name "Plaxel CD-205"; molecular weight 500) 1
00 g, polycaprolactone triol (manufactured by Daicel Chemical Industries, Ltd., trade name “Placcel 303”; molecular weight 3)
(00) was dissolved in 150 g of xylene to prepare a uniform solution (hereinafter referred to as solution (II)). The resulting solution (I) was heated to 90 ° C. with stirring, and solution (II) was added dropwise. After the completion of dropping, aging under stirring at 90 ° C. for 5 hours,
The urethanization reaction was completely terminated, and a moisture-curable composition having an unreacted isocyanate group was obtained.

The obtained moisture-curable composition was concentrated under reduced pressure to a solid content of 80% and then applied on a keren-treated iron plate and allowed to stand at room temperature for a whole day and night, which was excellent in xylene rubbing resistance and adhesiveness. A coating film was obtained. The initial gloss value of the coating film applied on this iron plate was 95%. A weather resistance test was conducted on the iron plate with the coating film using a sunshine weatherometer. The gloss value after 1000 hours was 80%, and the difference in color immediately after the coating film was formed and after 1000 hours after the weather resistance test. It was 1.0. Also,
The shape of the coating film surface was not much different from that immediately after the coating film was formed and was sufficiently smooth.

Example 2 First, 250 g of isophorone diisocyanate, 0.25 g of dibutyltin dilaurate, 2.5 g of triethylenediamine and 250 g of xylene were mixed at room temperature to prepare a uniform solution (hereinafter referred to as solution (I)). . On the other hand, polycarbonate diol (manufactured by Daicel Chemical Industries, Ltd.,
Product name "Plaxel CD-205"; molecular weight 500) 1
A solution of 100 g of xylene uniformly dissolved in 100 g of xylene (hereinafter referred to as a solution (II)), and 70 g of polycaprolactone triol (manufactured by Daicel Chemical Industries Ltd., trade name "Placcel 303"; molecular weight 300) 70 g of xylene
Solution uniformly dissolved in (hereinafter referred to as solution (III))
Was adjusted respectively. The obtained solution (I) was heated to 90 ° C. with stirring, and first, the solution (II) was added dropwise. The solution (III) was further added dropwise at 90 ° C. to the solution after the addition of the solution (II) was completed. 90 ℃ after solution (II) dropping
A moisture-curable composition 80, which is aged under stirring for 5 hours to completely terminate the urethanization reaction and which contains a mixture of di- and triisocyanates having unreacted isocyanate groups.
0 g was obtained.

The obtained moisture-curable composition was concentrated under reduced pressure to a solid content of 80% and then applied on a keren-treated iron plate and allowed to stand at room temperature for a day and night, which was excellent in xylene rubbing resistance and adhesiveness. A coating film was obtained. The initial gloss value of the coating film applied on this iron plate was 94%. A weather resistance test was carried out on the iron plate with the coating film using a sunshine weatherometer. The gloss value after 1000 hours was 82%, and the difference in color immediately after the coating film was formed and after 1000 hours after the weather resistance test. It was 0.9. Also,
The shape of the coating film surface was not much different from that immediately after the coating film was formed and was sufficiently smooth.

Example 3 Polycarbonate diol of Example 1 was replaced with 100 g of polycarbonate diol (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Nipporan 981"; molecular weight about 10).
00) was used in the same manner as in Example 1 to obtain a moisture-curable composition and a coating film having excellent xylene rubbing resistance and adhesiveness on an iron plate. The initial gloss value of the coating film applied on this iron plate was 95%. A weather resistance test was conducted on the iron plate with the coating film using a sunshine weatherometer. The gloss value after 1000 hours was 82%.
The color difference after 000 hours was 0.9. Further, the shape of the coating film surface was not much different from that immediately after the coating film was formed and was sufficiently smooth.

Example 4 First, 1.64 g of azobisbutyronitrile was uniformly dissolved in 64 g of n-butyl acrylate, and the resulting solution was dissolved in 153 g of bis (2-hydroxyethyl) disulfide.
The mixture was gradually added dropwise at 100 ° C. with stirring. After completion of the dropping, the mixture was further aged at the same temperature for 1 hour to complete the polymerization reaction, sufficiently purified and dehydrated, and then 217 g of OH-modified acrylic polymer having both ends OH modified with a molecular weight of about 4,500 was obtained. 100 g of the polycarbonate diol of Example 1
Instead, 200 g of the obtained polyacrylic diol was used to obtain a moisture-curable composition and a coating film excellent in xylene rubbing resistance and adhesiveness on an iron plate by the same operation as in Example 1. The initial gloss value of the coating film applied on this iron plate was 95%. A weather resistance test was carried out on the iron plate with the coating film using a sunshine weatherometer. The gloss value after 1000 hours was 82%, and the difference in color immediately after the coating film was formed and after 1000 hours after the weather resistance test. It was 0.9. Further, the shape of the coating film surface was not much different from that immediately after the coating film was formed and was sufficiently smooth.

Example 5 Instead of 100 g of the polycarbonate diol of Example 1, polysiloxane diol (Toray Dow Corning.
Silicone Co., Ltd., trade name "SF8427", molecular weight about 2400) 200 g was used to carry out the same operation as in Example 1 to form a moisture-curable composition and a coating film excellent in xylene rubbing resistance and adhesion on an iron plate. Got to. The initial gloss value of the coating film applied on this iron plate was 95%. Also,
When a weather resistance test was conducted on the iron plate with the coating film by a sunshine weatherometer, the gloss value after 1000 hours was 82%, and the color difference immediately after the coating film was formed and after 1000 hours after the weather resistance test was 0. It was 9. Further, the shape of the coating film surface was not much different from that immediately after the coating film was formed and was sufficiently smooth.

Example 6 Instead of 100 g of the polycarbonate diol of Example 1, polysiloxane diol (trade name SF8427) was used.
The same procedure as in Example 1 was performed using a mixture of 30 g of Toray Dow Corning Silicone Co., Ltd. having a molecular weight of about 2400) and 85 g of polycaprolactone diol (trade name: Praxel 205, Daicel Chemical Industries Ltd .; molecular weight of 500). Thus, a moisture-curable composition and a coating film having excellent xylene rubbing resistance and adhesiveness were obtained on an iron plate. The initial gloss value of the coating film applied on this iron plate was 95%.
A weather resistance test was conducted on the iron plate with the coating film by using a sunshine weatherometer.
The gloss value after 0 hours was 82%, and the color difference immediately after the coating film was formed and after 1000 hours of the weather resistance test was 0.9. Moreover, the shape of the coating film surface is not much different from that immediately after the coating film is formed,
It was smooth enough.

Example 7 To 100 g of the moisture-curing composition (solid content 80%) obtained by the same operation as in Example 1, 0.1 g of Tinuvin 292 (manufactured by Ciba-Geigy Co., Ltd.) as an antioxidant, And as a UV absorber, Tinuvin 900 (Japan Ciba-Geigy-
(Manufactured by Co., Ltd.) was added thereto, and the mixture was thoroughly stirred under dry nitrogen to completely dissolve it.
A coating film excellent in xylene rubbing resistance and adhesiveness was obtained on the iron plate by the same operation as in. The initial gloss value of the coating film applied on this iron plate was 95%. A weather resistance test was carried out on the iron plate with the coating film using a sunshine weatherometer. The gloss value after 2000 hours was 82%, and the color difference immediately after the coating film was formed and after 2000 hours after the weather resistance test had passed. It was 0.9. Further, the shape of the coating film surface was not much different from that immediately after the coating film was formed and was sufficiently smooth.

Example 8 100 g of the moisture-curing composition (solid content 80%) obtained by the same operation as in Example 2 was used, and 0.1 g of the same antioxidant as in Example 7 and 0. 1 g was added, and from the moisture-curing composition obtained by the same operation as in Example 7, a coating film excellent in xylene rubbing resistance and adhesiveness was obtained on an iron plate by the same operation as in Example 1. The initial gloss value of the coating film applied on this iron plate was 95%. A weather resistance test was conducted on the iron plate with the coating film using a sunshine weatherometer. The gloss value after 2000 hours was 82%.
The color difference after the elapse of time was 0.9. Further, the shape of the coating film surface was not much different from that immediately after the coating film was formed and was sufficiently smooth.

Example 9 To 100 g of the moisture-curing composition (solid content 80%) obtained by the same operation as in Example 3, 0.1 g of the same antioxidant as in Example 7 and 0. 1 g was added, and from the moisture-curing composition obtained by the same operation as in Example 7, a coating film excellent in xylene rubbing resistance and adhesiveness was obtained on an iron plate by the same operation as in Example 1. The initial gloss value of the coating film applied on this iron plate was 95%. A weather resistance test was conducted on the iron plate with the coating film using a sunshine weatherometer. The gloss value after 2000 hours was 82%.
The color difference after the elapse of time was 0.9. Further, the shape of the coating film surface was not much different from that immediately after the coating film was formed and was sufficiently smooth.

Example 10 To 100 g of the moisture-curing composition (solid content 80%) obtained by the same operation as in Example 4, 0.1 g of the same antioxidant as in Example 7 and 0. 1 g was added, and from the moisture-curing composition obtained by the same operation as in Example 7, a coating film excellent in xylene rubbing resistance and adhesiveness was obtained on an iron plate by the same operation as in Example 1. The initial gloss value of the coating film applied on this iron plate was 95%. A weather resistance test was conducted on the iron plate with the coating film using a sunshine weatherometer. The gloss value after 2000 hours was 82%.
The color difference after the elapse of time was 0.9. Further, the shape of the coating film surface was not much different from that immediately after the coating film was formed and was sufficiently smooth.

Example 11 To 100 g of a moisture-curing composition (solid content 80%) obtained by the same operation as in Example 5, 0.1 g of the same antioxidant as in Example 7 and 0. 1 g was added, and from the moisture-curing composition obtained by the same operation as in Example 7, a coating film excellent in xylene rubbing resistance and adhesiveness was obtained on an iron plate by the same operation as in Example 1. The initial gloss value of the coating film applied on this iron plate was 95%. A weather resistance test was conducted on the iron plate with the coating film using a sunshine weatherometer. The gloss value after 2000 hours was 82%.
The color difference after the elapse of time was 0.9. Further, the shape of the coating film surface was not much different from that immediately after the coating film was formed and was sufficiently smooth.

Example 12 To 100 g of the moisture-curing composition (solid content 80%) obtained by the same operation as in Example 6, 0.1 g of the same antioxidant as in Example 7 and 0. 1 g was added, and from the moisture-curing composition obtained by the same operation as in Example 7, a coating film excellent in xylene rubbing resistance and adhesiveness was obtained on an iron plate by the same operation as in Example 1. The initial gloss value of the coating film applied on this iron plate was 95%. A weather resistance test was conducted on the iron plate with the coating film using a sunshine weatherometer. The gloss value after 2000 hours was 82%.
The color difference after the elapse of time was 0.9. Further, the shape of the coating film surface was not much different from that immediately after the coating film was formed and was sufficiently smooth.

Comparative Example 1 VESTICOAT UT880 which is a polyester ether type urethane prepolymer containing polycaprolactone.
(Huls Co., NCO content 5.5% by weight) 100% by weight of 70% by weight xylene solution and VESTICOAT
UT647 (manufactured by Huls, NCO content 5.5% by weight) 44 parts by weight of 70% by weight xylene solution were mixed well,
By the same operation as in Example 1, a coating film having excellent xylene rubbing resistance and adhesiveness was obtained on an iron plate. The initial gloss value of the coating film applied on this iron plate was 95%. A weather resistance test was conducted on the iron plate with the coating film using a sunshine weatherometer. The gloss value after 1000 hours was 3%.
The color difference after 00 hours was 20.0. In addition, cracks and fine dent-like defects were observed on the coating film surface.

Comparative Example 2 In place of the polycarbonate diol of Example 1, polycaprolactone diol (manufactured by Daicel Chemical Industries, Ltd., trade name "Placcel CD-205"; molecular weight 500) was used.
The same procedure as in Example 1 was performed using 00 g to obtain a moisture-curable composition and a coating film having excellent xylene rubbing resistance and adhesiveness on an iron plate. The initial gloss value of the coating film applied on this iron plate was 95%. However, when a weather resistance test was conducted on the iron plate with the coating film using a sunshine weatherometer, the gloss value after 1000 hours was 40%, which means that the film immediately after the coating film formation and the weather resistance test 1000
The color difference after the lapse of time was 10.0. In addition, cracks and fine dent-like defects were observed on the coating film surface.

[0054]

The moisture-curable composition of the present invention is excellent not only in dispersibility of pigments, initial gloss and weather resistance but also in water resistance and long-term weather resistance. The present invention provides a curable composition which is particularly useful for heavy-corrosion coating applications because of its excellent durability and weather resistance.

Claims (11)

[Claims] 1. A moisture-curable composition comprising a modified polyisocyanate obtained by reacting at least one polyol selected from a polycarbonate polyol, an acrylic polyol, and a silicone polyol as a polyisocyanate. 2. The moisture-curable composition according to claim 1, wherein the average value of the residual isocyanate group per molecule of the modified polyisocyanate is 2.2 to 3.0. 3. The moisture curable composition according to claim 1, wherein the content of the modified polyisocyanate is 20 to 80% by weight based on the whole moisture curable composition. 4. The moisture curable composition according to claim 1, wherein the polycarbonate polyol is an aliphatic polycarbonate polyol. 5. The moisture-curable composition according to claim 1, wherein the polycarbonate polyol is an aliphatic polycarbonate diol. 6. The moisture curable composition according to claim 1, wherein the acrylic polyol is an acrylic diol. 7. The moisture curable composition according to claim 1, wherein the silicone polyol is an alkyl-substituted silicone polyol. 8. The moisture-curable composition according to claim 1, which contains an aliphatic polyester polyol-modified polyisocyanate obtained by reacting an aliphatic polyester polyol with a polyisocyanate. 9. The moisture curable composition according to claim 8, wherein the main component of the aliphatic polyester polyol is a polycaprolactone-based polyol resin. 10. The moisture-curable composition according to claim 8, wherein the aliphatic polyester polyol is an aliphatic polyester polyol having 3 or more hydroxyl groups in one molecule. 11. The moisture curable composition according to claim 1, wherein the polyisocyanate is an aliphatic diisocyanate or a polyaddition product thereof.