JP3925732B2 - Two-component room temperature curable urethane film waterproofing material composition - Google Patents

Description

  The present invention relates to a two-component room temperature curable urethane coating film waterproofing material composition.

In recent years, coatings made of polyurethane (hereinafter referred to as “urethane coatings”) have excellent adhesiveness, flexibility, weather resistance, etc., and thus have a wide range of industries such as architecture, civil engineering, automobiles, and telecommunications. Demand applications are increasing in the field. In particular, in the field of construction and civil engineering, urethane coatings are widely used as waterproofing materials, coating floor materials, casting materials, sealing materials and the like.
Such urethane coatings are classified into one-pack type (moisture curing type) and two-pack type (curing agent curing type). Examples of the two-part type include a two-part type polyurethane composition comprising a main agent containing a urethane prepolymer having an isocyanate group at the terminal and a curing agent containing a polyol, an amine compound and a curing catalyst. It is done.

Various studies have been made on such two-component polyurethane compositions with the aim of further improving performance. For example, Patent Document 1 discloses a two-pack type that is fast-curing but can take a sufficient pot life, has a sufficient hardness after curing, and gives a cured product with low surface tack. Polyurethane compositions aimed at providing polyurethane compositions are described.
The polyurethane composition described in Patent Document 1 contains a urethane prepolymer having an isocyanate group at the terminal, an organic polyvalent amine compound, a polyhydroxy compound, an organic acid, and a bismuth carboxylate compound, and the urethane composition The organic acid is contained in an amount of 0.5 × 10 ^{−3 to} 2.0 × 10 ⁻³ mol and the bismuth carboxylate compound is contained in an amount of 0.1 to 0.5 parts by mass with respect to 100 parts by mass of the prepolymer. However, it is a polyurethane composition for construction that does not use a thermoforming mold characterized by curing.
In addition, the polyurethane composition described in Patent Document 1 is a two-component type, a main component liquid containing a urethane prepolymer having an isocyanate group at the terminal as a main component, an organic polyvalent amine compound as a curing agent, and It is comprised with the hardening | curing liquid agent containing a polyhydroxy compound.
Patent Document 1 discloses that the polyurethane composition contains, as a filler, calcium carbonate, carbon black, clay, talc, titanium oxide, quicklime, kaolin, zeolite, persimmon earth, vinyl chloride paste resin, glass balloon, chloride. It is described that it is possible to contain a vinylidene resin balloon or the like.

  Balloons such as glass balloons and vinylidene chloride resin balloons mentioned as fillers in the polyurethane composition are generally used for the purpose of reducing the specific gravity of the polyurethane composition. When such a polyurethane composition containing a balloon is applied onto a concrete surface of a building rooftop, a veranda, a corridor, etc. (hereinafter referred to as “buildings”), for example, the resulting urethane coating film is Because it is lightweight, it can reduce the load on buildings.

Japanese Patent No. 2997511

However, when the present inventor examined, in order to further reduce the weight of the urethane coating film, when the above balloon was blended in an amount of 1% by mass or more with respect to the curing agent of the polyurethane composition, leveling properties (flatness of the urethane coating film) It was found that workability such as That is, when a polyurethane composition in which the balloon is blended in an amount of 1% by mass or more with respect to the curing agent of the polyurethane composition is used and applied to the surface of a building or the like with a trowel or the like, In many cases, a paint mark painted with a trowel or the like remains or unevenness tends to occur. Since such coating marks, unevenness, etc. remain as they are even after a lapse of time, the coating layer of the polyurethane composition is cured with the coating marks, unevenness, etc. on the surface. As a result, there was a problem that the appearance of the urethane coating film deteriorated.
Accordingly, an object of the present invention is to provide a two-component room temperature curable urethane coating film waterproofing material composition which is excellent in leveling properties even if it contains more balloons than conventional products.

In order to solve the above problems, the present inventor has intensively studied a two-component room temperature curable urethane coating film waterproofing material composition. As a result, the curing agent contains a specific balloon and a specific polyoxypropylene polyol compound. Thus, it has been found that even if the balloon is contained in a larger amount than the conventional product, the leveling property of the two-component room temperature curable urethane coating film waterproofing material composition can be made excellent.
The present inventor has completed the present invention based on these findings.

That is, the present invention provides the following (1) to ( 5 ).
(1) and main agent containing a urethane prepolymer, a two-liquid normal temperature curing type urethane waterproofing membrane material composition and a curing agent containing a polyoxypropylene polyol of ethylene oxide is added,
The main agent and / or wherein the curing agent, the maximum particle size 280μm following balloon resin hollow body is coated with an inorganic filler, the total amount of the main agent and the curing agent, 0.5 wt% A two-component room temperature curable urethane coating film waterproofing material composition.
(2) The two-component room temperature curable urethane coating film according to (1), wherein the resin-based hollow body is at least one selected from the group consisting of a phenol resin, a urea resin, polystyrene, saran, and a thermoplastic resin. Material composition.
(3) The thermoplastic resin is a polymer obtained from at least one monomer selected from the group consisting of vinyl chloride, vinylidene chloride, acrylonitrile, acrylate, methacrylate, styrenic monomer, vinyl acetate, butadiene, vinylpyridine, and chloroprene. The two-component room-temperature-curing urethane coating film waterproofing material composition according to (2) above.
(4) The two-component solution according to any one of (1) to (3), wherein the inorganic filler is at least one selected from the group consisting of calcium carbonate, titanium oxide, silicon oxide, talc, clay, and carbon black. Room temperature curable urethane film waterproofing material composition.
(5) The group in which the polyoxypropylene polyol to which ethylene oxide is added is composed of polypropylene glycol to which ethylene oxide is added, polyoxypropylene triol to which ethylene oxide is added, and polyoxypropylene tetraol to which ethylene oxide is added. The two-component room temperature curing urethane coating film waterproofing material composition according to any one of the above (1) to (4), which is at least one selected from:

  The two-component room temperature curable urethane coating film waterproof material composition of the present invention has excellent leveling properties even if it contains a large amount of balloons.

Hereinafter, the two-component room temperature curable urethane coating film waterproof material composition of the present invention will be described.
The two-component room temperature curable urethane coating film waterproof material composition of the present invention is
A base resin containing a urethane prepolymer, a two-liquid normal temperature curing type urethane waterproofing membrane material composition and a curing agent containing a polyoxypropylene polyol of ethylene oxide is added,
The main agent and / or wherein the curing agent, the maximum particle size 280μm following balloon resin hollow body is coated with an inorganic filler, the total amount of the main agent and the curing agent, 0.5 wt% A two-component room temperature curable urethane coating film waterproofing material composition.

  Even if the two-component room temperature curable urethane coating film waterproof material composition of the present invention contains more balloons than the conventional product, it has excellent leveling properties.

First, the main agent used for the two-component room temperature curable urethane coating film waterproof material composition of the present invention will be described.
The main agent used in the two-pack room temperature curable urethane coating film waterproof material composition of the present invention contains a urethane prepolymer.

  The urethane prepolymer may be any as long as it is used for a general two-component polyurethane composition. It is preferable that content of the isocyanate group of a urethane prepolymer is 0.5-5 mass% in a urethane prepolymer.

  The urethane prepolymer can generally be produced by reacting a polyisocyanate and a polyol.

Below, the polyol which is a raw material of a urethane prepolymer is demonstrated.
Examples of the polyol include polyether polyols, polyester polyols, polymer polyols, other polyols, and mixed polyols thereof.

  Examples of the polyether polyol include a product obtained by addition polymerization of one or more of ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran alkylene oxide to a compound having two or more active hydrogens.

Examples of the compound having two or more active hydrogens include polyhydric alcohols, amines, alkanolamines, and polyhydric phenols.
Examples of the polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, diethylene glycol, glycerin, hexanetriol, trimethylolpropane, and pentaerythritol.
Examples of amines include ethylenediamine and hexamethylenediamine. Examples of alkanolamines include ethanolamine and propanolamine. Examples of polyhydric phenols include resorcin and bisphenol.

Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polyoxypropylene triol , polyglycerin, polytetramethylene glycol, polytrimethylolpropane, polyhexanetriol, polybutanediol, polydihydroxyphenylmethane, polydihydroxyphenylpropane, Examples include polyoxypropylene glycol and polyoxybutylene glycol.

  Examples of the polyester polyol include condensates of polyhydric alcohols and polybasic carboxylic acids, condensates of hydroxycarboxylic acids and polyhydric alcohols, and lactone polymers.

  Examples of the polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, diethylene glycol, glycerin, hexanetriol, trimethylolpropane, and pentaerythritol.

  Examples of the polybasic carboxylic acid include saturated dicarboxylic acids such as glutaric acid, adipic acid, and azelaic acid; unsaturated dicarboxylic acids such as fumaric acid and maleic acid; phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Aromatic dicarboxylic acids such as dimer acids.

  Examples of the condensate of hydroxycarboxylic acid and polyhydric alcohol include a reaction product of castor oil and ethylene glycol, and a reaction product of castor oil and propylene glycol.

  Examples of the lactone polymer include those obtained by ring-opening polymerization of ε-caprolactam, α-methyl-ε-caprolactam, and ε-methyl-ε-caprolactam with an appropriate polymerization initiator.

  Examples of the polymer polyol include those obtained by graft polymerization of the above-described polyether polyol or polyester polyol with an ethylenically unsaturated compound (specifically, for example, acrylonitrile, styrene, methyl acrylate, methacrylate); -Polybutadiene polyol, 1,4-polybutadiene polyol, polyisoprene glycol and hydrogenated products thereof.

  Other polyols include, for example, polycarbonate polyol; acrylic polyol; 1,2-polybutadiene polyol, 1,4-polybutadiene polyol, and hydrogenated products thereof; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol. , Low molecular polyols such as pentanediol and hexanediol.

A polyol can be used individually or in combination of 2 or more types, respectively.
The number average molecular weight of the polyol is usually 100 to 10,000, and preferably 500 to 6,000.

The polyisocyanate that is another raw material of the urethane prepolymer will be described below.
Specific examples of the polyisocyanate include, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate (TDI), phenylene diisocyanate, xylene diisocyanate (XDI), diphenylmethane-4,4-diisocyanate (aromatic diisocyanate ( MDI), 1,5-naphthalene diisocyanate (NDI), tolidine diisocyanate (TODI) and their hydrogenated products;

As aliphatic diisocyanates, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI);
As alicyclic diisocyanate, 1-methyl-2,4-diisocyanatecyclohexane, 1-methyl-2,6-diisocyanatecyclohexane, dicyclohexylmethane diisocyanate;
Examples of the triisocyanate include triphenylmethane triisocyanate. These polyisocyanates can be used alone or in combination of two or more.

  And it does not restrict | limit in particular about manufacture of a urethane prepolymer. It can be produced according to the production conditions of a normal urethane prepolymer. Specific conditions include, for example, a method for producing a urethane prepolymer by reacting a polyol and a polyisocyanate at a reaction temperature of about 10 to 120 ° C. under normal pressure without using a catalyst or using a catalyst. Can be mentioned.

  Moreover, as a quantitative ratio of the polyol and the polyisocyanate when producing the urethane prepolymer, for example, an equivalent ratio of an isocyanate group in the polyisocyanate and a hydroxy group in the polyol (NCO group / OH group) is 1.5. It is preferable that it is -2.5.

Next, the curing agent used in the two-component room temperature curable urethane coating film waterproof material composition of the present invention will be described.
The curing agent of the two-component room temperature curable urethane coating waterproof material composition of the present invention is a curing agent containing polyoxypropylene polyol to which ethylene oxide is added.

Hereinafter, the polyoxypropylene polyol to which ethylene oxide is added will be described.
Examples of the polyoxypropylene polyol to which ethylene oxide is added include polypropylene glycol to which ethylene oxide is added, polyoxypropylene triol to which ethylene oxide is added, and polypropylene tetraol to which ethylene oxide is added.

Examples of the polyoxypropylene polyol to which ethylene oxide is added include a polyoxypropylene polyol having a hydroxyethyl group at at least one terminal (see the following formula (1)). Further, ethylene oxide can be randomly bonded in the main chain of the polyoxypropylene polyol .

A portion containing a hydroxyethyl group at at least one terminal of the polyoxypropylene polyol is represented, for example, by the formula (1).

—CH ₂ —CH (CH ₃ ) —O—CH ₂ —CH ₂ —OH (1)

In the formula (1), —CH ₂ —CH (CH ₃ ) —O— represents any one terminal in the structure of the polyoxypropylene polyol .

Here, since the hydroxy group of the hydroxyethyl group of the formula (1) is a primary alcohol, it is hardly affected by the surrounding steric hindrance.
On the other hand, the hydroxy group of the raw material polyoxypropylene polyol is a secondary alcohol and is affected by steric hindrance due to the α-position methyl group.

Therefore, the hydroxy group of the hydroxyethyl group of the formula (1) is less affected by steric hindrance and has higher hydrophilicity than the hydroxy group of the raw material polyoxypropylene polyol . Thereby, it is thought that the polyoxypropylene polyol to which ethylene oxide is added improves the wettability with respect to balloons, calcium carbonate used as a filler other than balloons, and the like. Accordingly, the affinity between the polyoxypropylene polyol to which ethylene oxide is added and the balloon or filler other than the balloon is increased, and the two-component room temperature curable urethane coating waterproof material composition of the present invention has excellent leveling. It is estimated that it will have sex.

The number average molecular weight of the polyoxypropylene polyol to which ethylene oxide is added is preferably 500 to 8000.
Such polyoxypropylene polyols to which ethylene oxide is added can be used alone or in combination of two or more.

And it is one of the suitable aspects that the polyoxypropylene polyol to which ethylene oxide is added is used as a mixture with the polyoxypropylene polyol which is the raw material.
The content of the polyoxypropylene polyol to which ethylene oxide is added is preferably 5 to 70% by mass in the total amount of the polyoxypropylene polyol to which ethylene oxide is added and the raw material polyoxypropylene polyol, and 5 to 60%. It is more preferable that it is mass%, and it is still more preferable that it is 5-50 mass%. When the content of polyoxypropylene polyols of ethylene oxide in the total amount of polyoxypropylene polyols and raw polyoxypropylene polyol ethylene oxide is added is added is low, as the polyoxypropylene polyols of ethylene oxide is added For example, what added about 1-2 ethylene oxide to the terminal of polyoxypropylene polyol is mentioned.

Polyoxypropylene polyols of ethylene oxide is added, as a mixture of polyoxypropylene polyols is a raw material thereof, for example, obtained by mixing a polyoxypropylene polyol and polyoxypropylene polyols of ethylene oxide is added mixture, and polyoxypropylene polyol is ethylene oxide obtained by the addition reaction of the raw material polyoxypropylene polyols with ethylene oxide is added, and a mixture of the raw material polyoxypropylene polyol.

The polyoxypropylene polyol to which ethylene oxide is added is not particularly limited for its production. For example, it can be performed according to a conventionally known method.

And the hardening | curing agent used in the two-component room-temperature-curing urethane coating film waterproofing material composition of the present invention contains an organic polyvalent amine compound in addition to the polyoxypropylene polyol to which the ethylene oxide is added. Is one of the preferred embodiments. By containing such an organic polyvalent amine compound, curability and physical properties are improved.

  Examples of organic polyvalent amine compounds include aliphatic diamines, aromatic diamines, and amine compounds having three or more amino groups in the molecule.

  Examples of the aliphatic diamine include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, and 1,7-heptane. Diamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine, hexamethylenediamine, trimethylhexamethylene Diamine, iminobispropylamine, methyliminobispropylamine, 1,5-diamino-2-methylpentane, isophoronediamine, 1,3-bisaminomethylcyclohexane, 1-cyclohexylamino-3-aminopropane, 3-aminomethyl -3,3,5-tri Chill - cyclohexylamine, dimethylene amines norbornane skeleton, m-xylylenediamine (MXDA), include hexamethylenediamine carbamate.

  Examples of the aromatic diamine include 3,3′-dichloro-4,4′-diaminodiphenylmethane (MOCA), 4,4′-diaminodiphenylmethane, 2,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,4-diaminophenol, 2,5-diaminophenol, o-phenylenediamine, m-phenylenediamine, p- Phenylenediamine, 2,3-tolylenediamine, 2,4-tolylenediamine, 2,5-tolylenediamine, 2,6-tolylenediamine, 3,4-tolylenediamine, methylthiotoluenediamine, diethyltoluenediamine Is mentioned.

  Examples of the amine compound having three or more amino groups in the molecule include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.

Among these, MOCA and methylthiotoluenediamine are preferable.
The organic polyvalent amine compounds can be used alone or in combination of two or more.
The amount of the organic polyvalent amine compound is preferably 1 to 10% by mass in the curing agent.

The main agent containing the urethane prepolymer and the curing agent containing polyoxypropylene polyol to which ethylene oxide is added include, for example, an isocyanate group in the main agent and a hydroxy group in the curing agent (the curing agent is organic polyvalent). When an amine is also contained, mixing may be performed so that the equivalent ratio [NCO group / (OH group + NH ₂ group)] to 0.8 to 1.5 is equal to the total of hydroxy group and amino group. preferable.

Next, the balloon will be described.
The balloon used is a balloon having a maximum particle size of 280 μm or less formed by coating a resin-based hollow body with an inorganic filler .

As trees fat-based hollow body, phenolic resins, urea resins, polystyrene, saran, and a thermoplastic resin. Among these, a thermoplastic resin hollow body is one of the preferred embodiments.

  Specific examples of the thermoplastic resin hollow body include, for example, encapsulating a liquid in the thermoplastic resin hollow body, heating the liquid, expanding the thermoplastic resin hollow body serving as an outer shell, Examples thereof include a thermally expandable thermoplastic resin hollow body obtained by vaporizing a liquid.

  A conventionally well-known thing can be used as a thermoplastic resin which comprises the outer shell component of the said thermoplastic resin hollow body. Specific examples of the thermoplastic resin include, for example, vinyl chloride, vinylidene chloride; acrylonitrile; acrylate, benzyl acrylate, norbornane acrylate; methacrylate, methyl methacrylate, norbornane methacrylate, trimethylolpropane trimethacrylate; styrenic monomer; vinyl acetate; Vinyl pyridine; a homopolymer of chloroprene, or a copolymer of two or more of these.

  A conventionally well-known thing can be used as a liquid included in the said thermoplastic resin hollow body. Specific examples of the liquid include, for example, n-pentane, isopentane, neopentane, butane, isobutane, hexane, petroleum ether as hydrocarbons; methyl chloride, methylene chloride, dichloroethylene, trichloroethane, and trichloroethylene as chlorinated hydrocarbons. It is done.

  The production of the hollow body is not particularly limited. For example, (1) Polymer 36, September (1987), p669, (2) Polymer 40, April (1991), p248-p251, (3) Japan Adhesion Association, Vol. 19 No. 11 (1983) p512-p517.

The inorganic filler will be described below.
The inorganic filler used is not particularly limited. For example, a conventionally well-known thing can be used. Specific examples include calcium carbonate, titanium oxide, silicon oxide, talc, clay, and carbon black. Of these, calcium carbonate is preferred. Such inorganic fillers can be used alone or in combination of two or more.

In addition, as the inorganic filler, a non-surface-treated and / or a surface-treated one can be used.
Examples of the inorganic filler that has not been surface-treated include those that have not been surface-treated with the above-mentioned inorganic filler.

The surface-treated inorganic filler is not particularly limited. For example, one of the preferred embodiments is that the above inorganic filler is surface-treated with at least one selected from the group consisting of fatty acids, resin acids and fatty acid esters. Of these, those surface-treated with fatty acids are preferred. Since the inorganic filler is surface-treated with at least one selected from the group consisting of fatty acids, resin acids and fatty acid esters, the wetness with the polyoxypropylene polyol to which ethylene oxide is added is improved, and the two-component room temperature The leveling property of a curable urethane coating film waterproofing material composition can be made excellent.

  Specific examples of fatty acids include, for example, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, melicic acid; Acid, sorbic acid; Examples of aromatic carboxylic acids include benzoic acid and phenylacetic acid. Of these, palmitic acid and stearic acid are preferable.

  Examples of the resin acid include abietic acid, neoabietic acid, pulstrated acid, pimaric acid, levopimaric acid, and isopimaric acid. Of these, abietic acid is preferable.

  For example, the fatty acid ester is preferably an ester of a higher fatty acid having 8 or more carbon atoms. Examples of the esters of higher fatty acids having 8 or more carbon atoms include lauryl palmitate, stearyl palmitate, lauryl stearate, stearyl stearate, tripalmitin, and tristearin. Of these, tristearin is preferable.

  The surface treatment amount of the fatty acid, resin acid or fatty acid ester is preferably 1.0 to 10% by mass in the inorganic filler after the surface treatment.

  And as a method of surface-treating the inorganic filler with at least one selected from the group consisting of fatty acids, resin acids and fatty acid esters as described above, for example, at least one selected from the group consisting of fatty acids, resin acids and fatty acid esters Examples include a method of adsorbing at least one selected from the group consisting of a fatty acid, a resin acid and a fatty acid ester on the surface of the inorganic filler by adding, kneading, spraying and immersing the seed into the inorganic filler.

  Further, a balloon coated with an inorganic filler that has not been surface-treated is subjected to surface treatment by adding, kneading, spraying, or immersing at least one selected from the group consisting of the above fatty acids, resin acids, and fatty acid esters. Depending on the case, the inorganic filler may be surface-treated. In this case, the hollow body may be surface-treated with the inorganic filler, or the entire balloon may be surface-treated.

In the balloon, the surface-treated inorganic filler may be, for example, in a state where the entire surface of the hollow body is coated or in a state where a part of the surface of the hollow body is coated.
The content of the surface-treated inorganic filler is preferably about 30 to 90% by mass in the total amount of the balloon. In such a range, since the balloon has an appropriate weight, it is easy to handle.

The maximum particle size of the balloon (the maximum particle size when the surface of the hollow body is coated with an inorganic filler) is 280 μm or less, preferably 30 to 270 μm, more preferably 30 to 250 μm. When it is in such a range, the leveling property of the two-component room temperature curable urethane coating film waterproofing material composition can be made excellent.
The balloons can be used alone or in combination of two or more.

  The balloon is not particularly limited for its production. For example, it can be produced according to a conventionally known method.

  The balloon is contained in the main agent and / or the curing agent. Especially, it is preferable that a balloon is contained in a hardening | curing agent. For example, it is preferable that the balloon is contained only in the curing agent or added separately to the main agent and the curing agent.

  The balloon is contained in an amount of 0.5% by mass or more based on the total amount of the main agent and the curing agent. The content of the balloon is preferably 0.5 to 10% by mass, and more preferably 0.5 to 8% by mass. The two-component room temperature curable urethane coating film waterproof material composition of the present invention has excellent leveling properties even when the balloon is contained in an amount of 0.5% by mass or more based on the total amount of the main agent and the curing agent. And a urethane coating film can be reduced in weight.

  In addition to these compounds, the two-pack room temperature curable urethane coating film waterproof material composition of the present invention has other additives, for example, a curing catalyst, a plasticizer, and other than the above balloons, as long as the object of the present invention is not impaired. Fillers, antioxidants, anti-aging agents, and pigments can be blended.

Examples of the curing catalyst include an organometallic catalyst.
Examples of the organometallic catalyst include dibutyltin dilaurate, dioctyltin laurate, zinc octylate, lead octenoate, organic bismuth compound, and lead octylate.
The curing catalysts can be used alone or in combination of two or more.

The amount of the curing catalyst is preferably 0.3 to 3% by mass in the curing agent. In addition, a curing catalyst may be mix | blended in a hardening | curing agent with the polyoxypropylene polyol to which ethylene oxide is added, and may be added directly at the time of mixing of a main ingredient and a hardening | curing agent.

  Examples of the plasticizer include diisononyl adipate (DINA), diisononyl phthalate (DINP), dioctyl phthalate (DOP), dibutyl phthalate (DBP), dilauryl phthalate (DLP), dibutyl benzyl phthalate (BBP), dioctyl adipate ( DOA), diisodecyl adipate (DIDA), trioctyl phosphate (TOP), tris (chloroethyl) phosphate (TCEP), tris (dichloropropyl) phosphate (TDCPP), propylene glycol adipate polyester, butylene glycol adipate polyester Can be mentioned. These plasticizers can be used alone or in combination of two or more.

  As a compounding quantity of a plasticizer, it is preferable that it is 10 mass parts or less with respect to 100 mass parts of urethane prepolymers.

Examples of the filler other than the balloon include calcium carbonate, carbon black, clay, talc, titanium oxide, quicklime, kaolin, zeolite, diatomaceous earth, fine powder silica and the like. Of these, calcium carbonate is preferred. These fillers can be used alone or in combination of two or more.
As a compounding quantity of a filler, it is preferable that it is 60 mass% or more in the whole quantity of a hardening | curing agent.

  Examples of the antioxidant include butylhydroxytoluene (BHT), butylhydroxytoluene anisole (BHA), diphenylamine, phenylenediamine, and triphenyl phosphite.

  Pigments are roughly classified into inorganic pigments and organic pigments. Specific examples of the inorganic pigment include, for example, titanium dioxide, zinc oxide, ultramarine, bengara; lithopone, lead, cadmium, iron, cobalt, aluminum sulfide, their hydrochlorides or their sulfates as metal oxides. It is done. Examples of organic pigments include azo pigments and copper phthalocyanine pigments.

  Since the two-component room temperature curable urethane coating film waterproofing material composition of the present invention is a two-component type, the main agent and the curing agent are mixed at the construction site, and the resulting composition is, for example, a metal iron and a roller. Can be used to paint.

The two-component room temperature curable urethane coating waterproof material composition of the present invention has excellent leveling properties even if it contains a large amount of balloons in order to further reduce the weight of the urethane coating. Therefore, the urethane coating film obtained by curing the two-component room temperature curable urethane coating film waterproofing material composition of the present invention has a flat surface, can have a beautiful appearance with no paint marks or unevenness, and is extremely lightweight. It is.
The thickness of the urethane coating film comprising the two-component room temperature curing urethane coating film waterproof material composition of the present invention is sufficient to be 1-2 mm. Even with such a thickness, it is sufficiently excellent in waterproofness, heat resistance, and mechanical strength.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

1. Preparation of Urethane Prepolymer 100 g of polyoxypropylene triol having a number average molecular weight of 4000 (T4000, manufactured by Asahi Glass Co., Ltd.) and 150 g of polyoxypropylene diol having a number average molecular weight of 2000 (D2000, manufactured by Asahi Glass Co., Ltd.) are placed in a reaction vessel, and viscosity is set. For adjustment, 15 g of diisononyl phthalate (DINP, manufactured by J. Plus) was added as a plasticizer, heated to 110 ° C., and dehydrated for 6 hours. Next, tolylene diisocyanate (Cosmonate T80, manufactured by Mitsui Takeda Chemical Co., Ltd.) was added thereto so that the equivalent ratio of NCO group / OH group was 1.98, and this was heated to 80 ° C. Time mixing, stirring, and urethane prepolymer were prepared. The content of NCO groups in the obtained urethane prepolymer was 3.0% by mass in the total amount of the urethane prepolymer.

2. Preparation of Curing Agent Each curing agent (curing agents 1 to 13) was prepared with the composition and blending ratio (parts by mass) shown in Table 1 below.

Each component shown in Table 1 is as follows.
Polyoxypropylene triol: number-average molecular weight of 5000 of polyoxypropylene triol (T5000, manufactured by Asahi Glass Co., Ltd.)
Ethylene oxide-added polyoxypropylene triol : A polyoxypropylene triol mixture containing 14 to 15% by mass of ethylene oxide-added polyoxypropylene triol obtained by adding ethylene oxide to the above T5000 (Sanniks FA703, Sanyo Chemical Industries, Ltd.) Made)
・ Calcium carbonate (Maruo Calcium)
・ 3,3'-dichloro-4,4'-diaminodiphenylmethane (manufactured by Ihara Chemical Industry Co., Ltd.)

・ Titanium oxide (Ishihara Sangyo Co., Ltd.)
・ Carbon (Mitsubishi Carbon Black MA220, manufactured by Mitsubishi Chemical Corporation)
Hydrophobic silica (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.)
・ Plasticizer (Diisononyl adipate: DINA, manufactured by Jay Plus)
・ Curing catalyst (Lead catalyst, Minico P-30, manufactured by Active Materials Chemical Company)
・ Solvent (Mineral Spirit, manufactured by Nippon Oil Corporation)

Balloon 1 (balloon having a maximum particle size of 100 μm formed by coating a vinylidene chloride hollow body with calcium carbonate surface-treated with a fatty acid);
Balloon 2 (balloon having a maximum particle size of 100 μm formed by coating a hollow surface of vinylidene chloride with untreated calcium carbonate);

-Balloon 3 (balloon having a maximum particle size of 150 μm formed by coating a vinylidene chloride hollow body with calcium carbonate surface-treated with a fatty acid);
Balloon 4 (balloon having a maximum particle size of 150 μm formed by coating a vinylidene chloride hollow body with untreated calcium carbonate);

Balloon 5 (balloon having a maximum particle size of 250 μm formed by coating a vinylidene chloride hollow body with calcium carbonate surface-treated with a fatty acid);
Balloon 6 (balloon having a maximum particle size of 250 μm formed by coating a vinylidene chloride hollow body with calcium carbonate not subjected to surface treatment);

Balloon 7 (balloon having a maximum particle size of 300 μm, which is obtained by coating a vinylidene chloride hollow body with calcium carbonate surface-treated with a fatty acid);
Balloon 8 (balloon having a maximum particle size of 300 μm formed by coating a hollow surface of vinylidene chloride with untreated calcium carbonate);

3. Examples (Examples 1-5, Comparative Examples 1-8)
The urethane prepolymer (100 parts by mass) obtained as described above and the above curing agents 1 to 13 (100 parts by mass) were mixed to obtain a urethane composition. Table 2 shows the equivalent ratio [NCO group / (NH ₂ group + OH group)] of the NCO group of the urethane prepolymer to the NH ₂ group and the hydroxy group in the curing agent and the specific gravity of the urethane composition.

4). Evaluation of leveling property The leveling property was evaluated about each obtained urethane composition. The evaluation method and evaluation criteria for leveling properties are shown below. Table 2 shows the evaluation results of each example and comparative example.
(1) Evaluation method: 90 g of each urethane composition described above was applied to a concrete surface having a width of 30 cm and a width of 30 cm with a comb-shaped iron and allowed to stand at 20 ° C. for 1 hour to be cured. The state of the urethane coating on the concrete was visually confirmed and evaluated immediately after application and 1 hour after application.

(2) Evaluation criteria The leveling property was evaluated according to the following evaluation criteria.
-5: The urethane coating is flat immediately after application and there is no trace or unevenness of the iron.
・ 4: There is no trace or unevenness of the iron, but it is slightly flat.
・ 3: There are no traces or irregularities on the iron, but it lacks flatness.
* 2: Traces and unevenness of the iron occur.
-1: It lacks in flatness, and a trace and unevenness of a iron arise.
・ 0: Comb eyes immediately after application and no change after 1 hour.

As is apparent from Table 2, Examples 1 to 5 have high leveling properties and excellent workability.
When Example 1 is compared with Comparative Example 4, the leveling property of Comparative Example 4 containing polyoxypropylene triol not added with ethylene oxide is inferior to that of Example 1.
Moreover, when Examples 1-5 are compared with Comparative Example 8, the leveling property of Comparative Example 8 using a balloon having a maximum particle size of 300 μm coated with calcium carbonate is higher than that of Examples 1-5. Inferior.
Moreover, when Example 3 and Comparative Examples 1-3 are compared, Example 3 has shown that leveling property is very high although there is much content of a balloon.

Claims (5)

A base resin containing a urethane prepolymer, a two-liquid normal temperature curing type urethane waterproofing membrane material composition and a curing agent containing a polyoxypropylene polyol of ethylene oxide is added,
The main agent and / or wherein the curing agent, the maximum particle size 280μm following balloon resin hollow body is coated with an inorganic filler, the total amount of the main agent and the curing agent, 0.5 wt% A two-component room temperature curable urethane coating film waterproofing material composition.   2. The two-component room temperature curable urethane coating waterproof material composition according to claim 1, wherein the resin-based hollow body is at least one selected from the group consisting of a phenol resin, a urea resin, polystyrene, saran, and a thermoplastic resin.   The thermoplastic resin is a polymer obtained from at least one monomer selected from the group consisting of vinyl chloride, vinylidene chloride, acrylonitrile, acrylate, methacrylate, styrenic monomer, vinyl acetate, butadiene, vinylpyridine and chloroprene. 2. A two-component room temperature curable urethane coating film waterproofing material composition according to 2.   The two-component room temperature curable urethane coating film according to any one of claims 1 to 3, wherein the inorganic filler is at least one selected from the group consisting of calcium carbonate, titanium oxide, silicon oxide, talc, clay, and carbon black. Waterproofing composition.   The polyoxypropylene polyol to which ethylene oxide is added is selected from the group consisting of polypropylene glycol to which ethylene oxide is added, polyoxypropylene triol to which ethylene oxide is added, and polyoxypropylene tetraol to which ethylene oxide is added. The two-component room temperature curable urethane coating film waterproofing material composition according to any one of claims 1 to 4, which is at least one kind.