JPH10183058A - Preparation of urethane coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for preparing a urethane coating material which can solve problems of the conventional urethane coating material, such as sedimentation of a powdery filler, caking, and thickening. SOLUTION: This process for preparing a urethane coating material for use in waterproof materials, such as roofs and wall surfaces, floor materials, pavement, sealants, coating materials, coatings and the like comprises mixing 60 pts.wt. liq. component, composed mainly of an isocyanate-contg. urethane prepolymer and an aldimine, with 40 pts.wt. fly ash having an average particle diameter of not more than 100μm as a powdery filler at the time of application.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to waterproof materials for roofs and walls, floor materials, paving materials, sealing materials, coating materials,
The present invention relates to a novel method for producing a urethane coating material used for a paint or the like.

[0002]

2. Description of the Related Art Urethane coating materials are excellent in mechanical strength, abrasion resistance, chemical resistance, weather resistance, and adhesion to a substrate, and can form a seamless coating film integrated with the substrate. It is widely used for waterproofing materials for roofs, waterproofing materials for wall surfaces, flooring materials, pavement materials, sealing materials, coating materials, paints, and the like. Urethane coating materials include urethane prepolymers having isocyanate groups (hereinafter referred to as urethane prepolymers), compounds having active hydrogen (hereinafter referred to as active hydrogen compounds), powder fillers, catalysts, stabilizers, plasticizers,
A composition comprising a thixotropic agent and other additives is generally used.
Particularly, the powder filler is a main component to be blended in an amount of about 20 to 50 parts by weight in the coating material, and plays an important role in improving the mechanical strength of the urethane coating material and improving the economic efficiency of the coating material.

[0003]

In a conventional urethane coating material, a liquid component and a powder filler are usually mixed in advance. However, when a powder filler is contained in the liquid component, sedimentation and caking of the powder filler occur due to a change over time, and there is a problem in storage stability of the product. Until now, as a method of solving this sedimentation and caking, the addition of a thixotropic agent imparts structural viscosity to prevent sedimentation and caking of the powder filler. However, when the thixotropic agent is added, there is a problem that the viscosity of the urethane coating material increases and the workability at the time of handling deteriorates. In addition, thixotropic agents are more expensive than other formulations and are economically problematic. Furthermore, if the storage of the powder filler compound is to be stored for a long period of time, it is impossible to completely prevent sedimentation and caking of the powder filler by any method other than the addition of a thixotropic agent. There was a problem in product storage. Furthermore, in the case of a one-component urethane coating material that has a moisture-curing mechanism, the curing reaction proceeds due to the effect of slight moisture remaining in the powder filler, and the viscosity increases with time, and finally the product cannot be used. However, no solution to this problem has been found so far, and a strong improvement has been demanded.

[0004]

Means for Solving the Problems The present inventors have intensively studied to solve these problems. As a result, in order to solve the problems of sedimentation and caking of the powder filler due to the inclusion of the powder filler in the raw material, and the problem of the effect of moisture in the powder filler, liquid components and powder It has been found that a method of separating the materials until the time of construction and mixing the two at the time of construction is a perfect method, and has been found to be more economical, and has completed the present invention. The present invention relates to a novel production method for obtaining a urethane coating material by mixing a liquid composition containing a urethane prepolymer and a powder filler at the time of construction.

That is, the present invention provides the following (1) to (6)
Is provided. (1) A method for producing a urethane coating material, comprising mixing a liquid composition containing a urethane prepolymer having an isocyanate group with a powder filler at the time of construction. (2) The method for producing a urethane coating material according to (1), wherein the powder filler has an average particle size of less than 100 μm. (3) The liquid composition is a liquid composition containing a urethane prepolymer having an isocyanate group, and a blocked amine that does not substantially react with the isocyanate and generates a primary or secondary amino group with water. The method for producing a urethane coating material according to (1) or (2), wherein (4) The method for producing a urethane coating material according to (3), wherein the block amine is aldimine. (5) The liquid composition comprises a liquid component containing a urethane prepolymer having an isocyanate group and a liquid component containing a compound having active hydrogen.
The method for producing a urethane coating material according to (1) or (2), wherein the liquid is mixed during construction. (6) The method for producing a urethane coating material according to any one of (1) to (5), wherein the powder filler is fly ash.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The liquid composition of the present invention is a component of a liquid urethane coating material containing no powder filler. All or a part of the liquid composition contributes to the curing reaction, and the powder filler does not contribute to the curing reaction. The present invention can be applied to any of the following curing mechanisms: (1) a mechanism based on the reaction between isocyanate and active hydrogen, (2) a mechanism based on moisture curing of isocyanate, and (3) a mechanism using blocked amine.

The urethane prepolymer having an isocyanate group used in the present invention refers to an isocyanate compound and a known compound having two or more active hydrogens in one molecule such as a polyol or an amine compound, which is obtained by a known method. The reaction was performed so that the group remained. That is, it is produced by reacting an isocyanate compound with a compound having active hydrogen at 100 ° C. for several hours. The isocyanate group content is preferably from 0.3 to 20.0% by weight, and particularly preferably from 0.5 to 15.0% by weight.

Specific examples of the isocyanate compound used herein include 1) tolylene diisocyanate (including various mixtures of isomers), diphenylmethane diisocyanate (including various mixtures of isomers), 3,3 ′
-Dimethyl-4,4'-biphenylene diisocyanate, 1,4-phenylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, naphthylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, hydrogen Xylene diisocyanate, 1,4-cyclohexyl diisocyanate, 1-methyl-2,4-diisocyanato-cyclohexane, 2,4,4-trimethyl-
Diisocyanates such as 1,6-diisocyanato-hexane; 2) 4,4 ′, 4 ″ -triphenylmethane triisocyanate; tris (4-phenyl isocyanato)
Triisocyanates such as thiophosphate, etc. 3)
Polyfunctional isocyanates such as urethane-modified isocyanates, isocyanurate-modified products, carbodiimidized-modified products, buret-modified products, crude tolylene diisocyanate, and polymethylene / polyphenylisocyanate.

Further, the compound having two or more active hydrogens in one molecule as used herein means two or more hydroxyl groups, one or more amino groups, two or more mercapto groups, Is a compound having a hydroxyl group and an amino group,
Or a compound having a hydroxyl group and a mercapto group, for example, water, ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, polyhydric alcohols such as sucrose, aniline, Range amine,
Aromatic amines such as p, p'-diamino-diphenylmethane, aliphatic amines such as ethylenediamine, ethanolamine, diethanolamine or alkanolamines and the above-mentioned compounds having two or more active hydrogens in one molecule thereof or Polyether polyols obtained by addition polymerization of propylene oxide or propylene oxide and ethylene oxide to a mixture of the compounds of the above compounds, polyether amine compounds obtained by converting hydroxyl groups of the polyether polyols to amino groups, polyether polyols Tetramethylene ether polyols, polycarbonate polyols, polycaprolactone polyols, polyester polyols such as polyethylene adipate, polybutadiene polyols, higher fatty acids such as castor oil Polymer polyols obtained by grafting vinyl monomers to esters, polyether polyols or polyester polyols, compounds obtained by copolymerizing known ethylenically unsaturated monomers having at least one active hydrogen in one molecule And ethers having a mercapto group.

The block amine used in the present invention includes aldimine, oxazolidine, enamine, polyketimine, β-lactam and the like, and at least one of them or a mixture of two or more thereof can be used. The blocked amine has a ratio of the number of amino groups of the amine compound generated by hydrolysis to the number of isocyanate groups contained in the urethane prepolymer of 0.5 to 2.0,
It is preferably obtained by mixing at a ratio of 0.7 to 1.5. Among them, the use of aldimine is the most preferable because it is excellent in the storage stability of the liquid composition, the curability of the urethane coating material, and the performance balance of the cured product properties.

The aldimine is represented by the following general formula (1):

[0012]

Embedded image (Wherein, X represents an aryl group having 6 to 15 carbon atoms).
Y represents a divalent or trivalent hydrocarbon group having 2 to 15 carbon atoms or a divalent or trivalent polyoxyalkylene group having a molecular weight of 70 to 6000. n represents 2 or 3. The amine compounds used in the production of aldimines include:
1) Aliphatic diamines such as ethylenediamine, 1,3-diaminopropane, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, decamethylenediamine, 4,4′-diaminodicyclohexylmethane, isophoronediamine, bis Aminomethylcyclohexane, 2,5- or 2,6-
Diamino methyl bicyclo [2.2.1] heptane, diaminocyclohexane, 3 (4), 8 (9) - bis (aminomethyl) - tricyclo [5.2.1.0 ^2.6] alicyclic diamines decane, Propylene oxide and / or aromatic diamine such as diaminodiphenylmethane, diaminodiphenylether, xylylenediamine, phenylenediamine, 3,5-diethyltoluene-2,4- or 2,6-diamine, water, ethylene glycol, propylene glycol, etc. Diamines such as polyoxyalkylenediamines obtained by converting hydroxyl groups of polyoxyalkylene glycols obtained by addition polymerization of ethylene oxide to amino groups; 2) 1,3,5-tris (aminomethyl) benzene; , 3,5-Tris (aminomethyl) cyclohexane Of polyoxyalkylene triols obtained by addition polymerization of propylene oxide and / or ethylene oxide to triamine, glycerin, trimethylolpropane, etc., and triamines such as polyoxyalkylene triamine obtained by converting hydroxyl groups to amino groups. is there.

The aldehyde to be reacted with the above amine compound includes, for example, benzaldehyde, o-tolualdehyde, m-tolualdehyde, p-tolualdehyde,
4-ethylbenzaldehyde, 4-propylbenzaldehyde, 4-butylbenzaldehyde, 2,4-dimethylbenzaldehyde, 2,4,5-trimethylbenzaldehyde, p-anisaldehyde, p-ethoxybenzaldehyde and the like.

The aldimine represented by the general formula (1) is subjected to an azeotropic dehydration reaction of the above-mentioned amine compound and the above-mentioned aldehyde with an acid catalyst using a solvent such as toluene or xylene. The reaction is obtained by continuing the reaction until the distillation of water into the water drop separator stops. The ratio of the above-mentioned amine compound to the above-mentioned aldehyde is suitably from 1 to 2 equivalents of the aldehyde to 1 equivalent of the amine.

The powder filler used in the present invention is a major component contained in the urethane coating material in an amount of at least 10% by weight, and is added in a small amount to the coating material for the purpose of coloring, imparting thixotropy, and the like. Powder additives are not included. Known powder fillers can be used. Specific examples of the powder filler include oxides (silica, alumina, zirconia, iron oxide, titanium oxide, magnesia, etc.), carbonates (calcium carbonate, magnesium carbonate, zinc carbonate, etc.), hydroxides ( Aluminum hydroxide, magnesium hydroxide, etc.), silicates (glass, kaolin, clay, talc, fly ash, mica, wollastonite, etc.), sulfates (calcium sulfate, barium sulfate, etc.),
Carbon (carbon black, graphite, etc.), titanate (potassium titanate, barium titanate, etc.), nitride (aluminum nitride, silicon nitride, etc.), carbide (silicon carbide, titanium carbide, etc.), phosphate (calcium phosphate, There are inorganic powder fillers such as ferrite (barium ferrite, calcium ferrite) and the like, and organic powder fillers of various resin powders such as hard urethane, phenol resin and polyvinyl chloride. These can be used alone or in combination of two or more.

The particle size of the powder filler affects the strength of the cured product. If the particle size is large, the strength of the cured product tends to decrease, so the particle size of the powder filler is preferably 100 μm.
m, more preferably 50 μm or less.

The amount of the powder filler is 10% by weight in the coating material.
Not less than 70 parts by weight and more preferably not more than 2 parts by weight.
It is not less than 0% by weight and not more than 60% by weight. If the amount of the powder filler is less than 10% by weight in the coating material, the strength of the cured product will be low, and if the amount of the powder filler exceeds 70% by weight, the elongation of the cured product will be reduced and the physical property balance will be poor. There is a tendency.

In the present invention, since the powder filler is mixed at the time of application, the powder filler can be easily mixed and dispersed in the liquid composition, the viscosity rise after mixing is small, and the cured product has high strength and high elongation. Body fillers are preferred. Among them, fly ash is preferred. Fly ash is a spherical filler generated by the combustion of fine coal powder used in a thermal power plant.The fly ash can be easily mixed and dispersed in a liquid component, and the viscosity increase after the mixed and dispersed is small. Since the urethane cured product to which the fly ash is added has an excellent balance between the physical properties of strength and elongation, fly ash is particularly preferred as the powder filler used in the present invention, and is particularly preferred.

The catalysts, stabilizers, plasticizers, adhesion promoters and other auxiliaries used in the present invention will be described.

Specific examples of the curing catalyst used in the present invention include, for example, dibutyltin dilaurate, lead octylate, stannas octoate, iron octoate,
Metal salts of carboxylic acids such as bismuth octoate and bismuth neodecaate; tertiary amine compounds; imidazole compounds;

Examples of the plasticizer used in the present invention include:
Specific examples include dioctyl phthalate, dibutyl phthalate, dilauryl phthalate, butylbenzyl phthalate, dioctyl phthalate, dioctyl adipate, diisodecyl adipate, diisodecyl phthalate, trioctyl phosphate, and chlorinated paraffin.

Examples of the solvent used in the present invention include:
Specifically, aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane, heptane and octane; petroleum solvents from gasoline to kerosene fraction; esters such as ethyl acetate and butyl acetate; And ketones such as methyl ethyl ketone and methyl isobutyl ketone, and ether esters such as cellosolve acetate and butyl cellosolve acetate.

Examples of the adhesion-imparting agent include silane couplers and titanate couplers. Further, examples of the coloring agent include pigments (carbon black, titanium white, red iron oxide, shinkasha red, fast red,
Quinacridone red, cyanine blue, cyanine green, chrome green, ocher, titanium yellow, first yellow, etc.), dyes and the like.

Examples of the stabilizer include hindered phenol compounds, triazole compounds, hindered amine compounds and the like. Further examples of thixotropic agents include colloidal silica, fatty acid amide wax, aluminum stearate, surface-treated bentonite, polyethylene short fiber,
Phenolic short fibers. Examples of antifoaming agents include silicone compounds.

As the curing mechanism of the urethane coating material of the present invention, (1) a mechanism by a reaction between an isocyanate compound and an active hydrogen compound (hereinafter referred to as a mechanism by a reaction between an isocyanate and an active hydrogen), and (2) a part of the isocyanate compound is air Reacting with water in the solution to form an amine compound, and reacting the resulting amine compound with an isocyanate compound (hereinafter referred to as a mechanism by moisture curing of isocyanate); A block amine compound (hereinafter referred to as a block amine) which forms a primary or secondary amino group is caused to coexist, and the blocked amine reacts with moisture in the air to form an amine compound. Reaction-based (hereinafter referred to as an apparatus using a block amine) It is roughly divided into three) of.

(1) When a mechanism based on the reaction between isocyanate and active hydrogen is used, the liquid composition is essentially composed of a liquid component containing a urethane prepolymer and a liquid component containing an active hydrogen compound. When a mechanism based on moisture curing of isocyanate is used, a liquid component containing a urethane prepolymer is essential, and when a mechanism using (3) a blocked amine is used, a liquid component containing a urethane prepolymer and a blocked amine is essential. is there. Therefore, (1) a liquid component is used in the case of using a mechanism by reaction between isocyanate and active hydrogen, (2) a liquid component is used in the case of using (2) a mechanism by moisture curing of isocyanate, and (3) a liquid component is used in the case of using a block amine. It becomes liquid,
These liquid components can be further divided into a plurality of liquids to obtain a configuration of two liquids or three or more liquids.

(1) In the case where a mechanism based on the reaction between isocyanate and active hydrogen is used, the number of liquid components is two or more, so that the number of mixing steps is disadvantageous as compared with the case where another curing mechanism is used. (2) When a mechanism based on moisture curing of isocyanate is used, the liquid component can be composed of only one liquid component and has an advantage of easy handling. When reacting to produce an amine compound, carbon dioxide gas is by-produced, and this carbon dioxide gas may easily cause problems such as foaming of a cured product. (3) In the mechanism using the block amine, the liquid component is 1
In addition to the advantage that it can be composed of only liquid components and is easy to handle, it also has the feature that no problems such as foaming of the cured product occur because no carbon dioxide gas is generated during the curing process. In the present invention, a liquid component having a composition using a curing mechanism utilizing a blocked amine is most preferred. (3) When a curing mechanism using a block amine is used, the curing reaction mainly proceeds from the surface of the coating material because the curing reaction is caused by moisture in the air, and in winter when the temperature and humidity are low, it takes time to cure the inside of the coating material. Will be applied.
In the present invention, since it is possible to add water to the liquid component and the powder filler at the time of construction, the addition of water allows the curing to proceed uniformly in the coating material, and furthermore, the curing is performed by adjusting the amount of water added. It is optionally possible to adjust the time.

When any of the curing mechanisms is used, a known additive (curing catalyst, plasticizer, plasticizer, plasticizer, etc.) is added to the liquid composition for the purpose of adjusting the curability, the viscosity of the coating material, the coloring, the resistance, and the thixotropy. Solvents, adhesion promoters, colorants, defoamers,
Stabilizers, thixotropic agents, etc.). Furthermore, it is also possible to add additives at the time of construction, instead of adding them to the liquid composition in advance.

When the liquid composition is one liquid and the filler is one type, the liquid composition and the powder filler are mixed at the time of construction to produce a urethane coating material. When the liquid composition is two or more liquids, or when additives are added at the time of construction, or when two or more kinds of powder fillers are used, three or more components are mixed, but these mixtures may be mixed in any order. It is feasible.

In the urethane coating material of the present invention, when mixing the liquid composition and the powder filler at the time of application, it is desirable to use a stirrer for efficiently stirring and mixing in a short time. A commonly used propeller type hand stirrer (product example: Ryoubi Power Mixer) can also be used, but the stirring efficiency has been further improved. Simultaneous scraping and mixing of the can wall with a stirrer of the type that mixes with a small propeller stirrer at the same time as dropping (product example: Hard mixer 18LM type manufactured by Nippon Sosei Kogyo Co., Ltd.) or L-type stirring blade under reduced pressure Mixer (product example: Vacuum hard mixer UV-2 manufactured by Nippon Sosei Co., Ltd.)
0L type) is preferred. The method of applying the urethane coating material of the present invention to a body such as a concrete base can be carried out by a conventional method. For example, iron, rake,
It can be performed by a method using a roller, a spray, or the like.

[0031]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the examples, “parts” indicates “parts by weight”.

[Synthesis Example of Urethane Prepolymer] Synthesis Example 1 In a reaction vessel equipped with a stirrer and a thermometer, 102 parts of 2,4-tolylene diisocyanate as a diisocyanate, and polyoxypropylene triol (Triol-500)
0, molecular weight 5000) 898 parts, and under a nitrogen stream,
Reaction at 100 ° C. for 10 hours, urethane prepolymer P
-1 (terminal NCO group was 2.5% by weight).

Synthesis Example 2 In the same manner as in Synthesis Example 1, 100 parts of tolylene diisocyanate having an isomer ratio of 2,4: 2,6 is 65:35 and polyoxypropylene triol (molecular weight: 5,000) 9
00 parts from the urethane prepolymer P-2 (terminal NCO
(2.7% by weight).

Synthesis Example 3 In the same manner as in Synthesis Example 1, urethane prepolymer P-3 (terminal NCO group: 2.4 parts by weight) was prepared from 141 parts of 4,4′-diphenylmethane diisocyanate and 859 parts of polyoxypropylene triol (molecular weight: 5000). %).

[Synthesis Example of Block Amine] Synthesis Example 4 88 parts (2.0 parts) of tetramethylenediamine was placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a water separator.
Equivalent), 0.1 part of formic acid and 500 parts of toluene, and mixed at room temperature under a nitrogen stream. After about 10 minutes, 300 parts (2.5 equivalents) of p-tolualdehyde was added to the dropping funnel for about 3 minutes.
It was dropped in 0 minutes. The reaction was continued for about 6 hours under reflux until water distillation stopped. The distilled water was 36 parts. Next, the external temperature was set to 150 ° C. Subsequently, toluene and unreacted p-tolualdehyde were distilled off. The reaction product (A-1) obtained after the distillation was 290 parts. In addition, as a result of measuring the infrared absorption spectrum of the obtained reaction product,
A characteristic absorption spectrum of -N = CH- was observed at 40 cm ^-1 . Dialdimine A-1 has an amine value of 381 mg KOH
/ G and a yellow liquid at room temperature.

Synthesis Example 5 1,4-bis {3,3-dimethyl-2-oxo-1- [3- (2- (2-ethoxyethoxy) ethoxycarbonylaminomethyl) benzyl] according to JP-A-2-168
Azetidin-4-yl @ piperazine was synthesized to obtain β-lactam.A-2 (amine value: 133 mgKOH / g).

Example 1 Example 1 45.3 parts of urethane prepolymer P-1, 4.1 parts of aldimine A-1, 5.0 parts of DOP, 5 of xylene
Octylic acid, and 0.2 part of Tinuvin B-75 (manufactured by Ciba Geigy) were mixed to prepare a liquid composition G-1. The obtained liquid composition G-1 showed no precipitation of a solid component, no separation of a liquid, and the like after storage at room temperature for one year, and a slight increase in viscosity. 60.1 parts of the liquid composition G-1 was mixed with fly ash (Onoda Super Flow SF- # manufactured by Chichibu Onoda)
40 parts were stirred and mixed under reduced pressure for 10 minutes using a vacuum hard mixer UV-20L manufactured by Nippon Sosei Co., Ltd. The viscosity after mixing is 8000 cP
s (25 ° C.), and had good workability for ironing and the like. Physical properties of the cured product are hardness 66 (Shore A),
Tensile strength 29 (kgf / cm ² ), elongation 820 (%),
The tear strength was 18 (kgf / cm), which was a good balance of physical properties as a urethane coating material. Liquid composition G
After storing -1 for 1 year at room temperature, a cured product was produced in the same manner. However, there was only a slight decrease in physical properties and no problem was observed in use.

Examples 2 to 7 Cured products were produced in the same manner as in Example 1 with the mixing ratios and stirring and mixing methods shown in Table 1. All of the cured products had good physical property balance as urethane coating materials.

Example 8 Tinuvin B-7 was added to 50 parts of urethane prepolymer P-2.
5 (manufactured by Ciba Geigy) and 0.5 part of a liquid component G-8.
1 was adjusted. The resulting liquid component G-81 showed a slight decrease in the concentration of terminal NCO groups and a slight increase in viscosity after storage at room temperature for one year. Polyoxypropylene diol (Diol-3)
2,4,4'-methylenebis (2-chloroaniline) (MOCA) in 26.8 parts.
0 parts were dissolved, and 0.2 parts of lead octylate and 10 parts of dioctyl phthalate (DOP) were added to prepare a liquid component G-82. The obtained liquid component G-82 was a yellow transparent liquid, and after storage at room temperature for one year, no precipitation of the solid component, no separation of the liquid, and the like were observed, and no change was observed in the liquid viscosity. Liquid component G-81
50.5 parts, liquid component G-82 39 parts, calcium carbonate (Shiraishi calcium whiten SSB, average particle size 1.3 μm) 30 parts, kaolin clay (Tsuchiya kaolin N, N-kaolin clay, average particle size 6) (10 μm) was stirred and mixed under reduced pressure for 10 minutes using a vacuum hard mixer UV-20L manufactured by Nippon Sosei. The viscosity after mixing was 8300 cP (25 ° C.), and the workability was good for ironing and the like. The physical property value of the cured product is hardness 69 (S
holeA), tensile strength 35 (kgf / cm ² ), elongation 800 (%), and tear strength 17 (kgf / cm).
It was a good balance of physical properties as a urethane coating material. Liquid component G-81 and liquid component G-82 at room temperature
After storage for a year, a cured product was produced in the same manner. However, there was only a slight decrease in physical properties and no problem was found in use.

Example 9 50 parts of urethane prepolymer P-3, 5 parts of DOP,
Xylene 5 parts, Tinuvin B-75 (made by Ciba-Geigy)
0.5 part was mixed to prepare a liquid composition G-9. The liquid composition G-9 showed no precipitation of a solid component, no separation of the liquid, and the like after storage at room temperature for one year, and a slight increase in viscosity. 60.5 parts of liquid component G-9, 30 parts of calcium carbonate (whiten SSB made of Shiraishi calcium), and 10 parts of kaolin clay (N, N-kaolin clay made by Tsuchiya Kaolin) were vacuum hard mixer UV-20L type manufactured by Nippon Sosei Co. 1
The mixture was stirred and mixed under reduced pressure for 0 minutes. The viscosity after mixing is 150
It was 00 cP (25 ° C.), and there was no problem in workability of ironing. The physical property value of the cured product is hardness 65 (Shor
eA), tensile strength 25 (kgf / cm ² ), elongation 740
(%), Tear strength 16 (kgf / cm), and a good balance of physical properties as a urethane coating material. After the liquid component G-9 was stored at room temperature for one year, a cured product was produced in the same manner. However, there was only a slight decrease in physical properties and no problem was found in use.

Example 10 A liquid component G was prepared in the same manner as in Example 1 at the compounding ratio shown in Table 2.
-10 was adjusted. 0.2 parts of water was added to 60.1 parts of the liquid component G-10, and 40 parts of fly ash (Onoda Super Flow SF- # 5000 manufactured by Chichibu Onoda, average particle size 8 μm) was mixed with a vacuum hard mixer UV-20L manufactured by Nippon Sosei. The mixture was stirred and mixed under reduced pressure for 10 minutes. The viscosity after mixing was 9000 cP (25 ° C.), and the workability was good for ironing and the like. The physical property value of the cured product is hardness 66 (Sh
ore A), tensile strength 31 (kgf / cm ² ), elongation 8
00 (%), tear strength 18 (kgf / cm). It was a good balance of physical properties as a urethane coating material.

Examples 11 to 12 Cured products were produced in the same manner as in Example 1 with the mixing ratios and stirring / mixing methods shown in Table 2. In Example 11, calcium carbonate having an average particle size of 40 μm (G # 100 manufactured by Sankyo Milling Co., Ltd.)
In Example 12, calcium carbonate having an average particle size of 250 μm (K # 1 manufactured by Sankyo Mills) was used as the powder filler. As the average particle size of the powder filler increased, the elongation of the cured product decreased significantly.

COMPARATIVE EXAMPLE 1 45.3 parts of urethane prepolymer P-1, 4.1 parts of aldimine A-1, 5.0 parts of DOP, and 5 parts of xylene were placed in a reaction vessel equipped with a stirrer and a thermometer under a stream of dry nitrogen.
And 0.2 parts of octylic acid, and the mixture was stirred and mixed at room temperature for 5 minutes. Calcium carbonate (Shiraishi calcium whiten S
SB) 30 parts, Kaolin clay (N, N made by Tsuchiya Kaolin)
-Kaolin clay), and the mixture was stirred at room temperature for 30 minutes and further at room temperature under reduced pressure for 20 minutes to obtain a urethane coating material H-1. When the urethane coating material H-1 was stored at room temperature for one year, sedimentation and caking of the powder filler were observed, and the viscosity was remarkably increased, so that it could not be used as a urethane coating material.

Comparative Example 2 A polyoxypropylene diol having a molecular weight of 3000 (Di) was placed in a reaction vessel equipped with a stirrer and a thermometer under a stream of dry nitrogen.
(ol-3000) 2.0 parts of 4,4′-methylenebis (2-chloroaniline) (MOCA) was inserted into 26.8 parts of the mixture, and the mixture was stirred at 80 ° C. for 10 minutes to dissolve MOCA. 4
After cooling to 0 ° C., 0.2 part of lead octylate and 10 parts of dioctyl phthalate (DOP) were added and stirred for 5 minutes, and then calcium carbonate (whiten SSB made of Shiroishi calcium) 30
And 10 parts of kaolin clay (N, N-kaolin clay made by Tsuchiya Kaolin) were inserted and stirred at room temperature for 30 minutes, and further stirred at room temperature under reduced pressure for 20 minutes to obtain a urethane coating material curing agent H-2. . When the urethane coating material curing agent H-2 was stored at room temperature for one year, sedimentation and caking of the powder filler were observed, and the urethane coating material could not be used.

Comparative Example 3 50 parts of urethane prepolymer P-3, 5 parts of DOP were placed in a reaction vessel equipped with a stirrer and a thermometer under a stream of dry nitrogen.
Xylene (5 parts) was inserted and mixed by stirring at room temperature for 5 minutes. Calcium carbonate (Shiraishi calcium whiten SSB) 3
0 parts and 10 parts of kaolin clay (N, N-kaolin clay manufactured by Tsuchiya Kaolin) were added, and the mixture was stirred at room temperature for 30 minutes and further stirred at room temperature under reduced pressure for 20 minutes to obtain a urethane coating material H-3. When the urethane coating material H-3 was stored at room temperature for one year, sedimentation and caking of the powder filler were observed, and the viscosity was significantly increased, so that the urethane coating material could not be used.

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

According to the present invention, by mixing a powder composition with a liquid composition containing a urethane prepolymer at the time of construction, a powder filler of a urethane coating material in which a conventional powder filler is mixed in advance is used. Problems such as sedimentation, caking, and thickening of water can be solved. The liquid composition and the filler of the present invention can be stored for a long period of time.

Claims (6)

[Claims] 1. A method for producing a urethane coating material, comprising mixing a liquid composition containing a urethane prepolymer having an isocyanate group with a powder filler at the time of construction. 2. The method for producing a urethane coating material according to claim 1, wherein the average particle diameter of the powder filler is less than 100 μm. 3. A liquid composition comprising a urethane prepolymer having an isocyanate group and a block amine which does not substantially react with the isocyanate and generates a primary or secondary amino group with water. The method for producing a urethane coating material according to claim 1 or 2, wherein: 4. The method for producing a urethane coating material according to claim 3, wherein the block amine is aldimine. 5. A liquid composition comprising a liquid component containing a urethane prepolymer having an isocyanate group and a liquid component containing a compound having active hydrogen,
The method for producing a urethane coating material according to claim 1 or 2, wherein the two liquids are mixed at the time of construction. 6. The method for producing a urethane coating material according to claim 1, wherein the powder filler is fly ash.