JP2003064349A - Polyurethane-based coating film waterproof material and construction method for coating film-waterproofing using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyurethane-based coating film waterproof material excellent in curability, coated film externals after curing, mechanical strength of the coating film and adhesion to substrate and topcoat. SOLUTION: This polyurethane-based coating film waterproof material is obtained by using a polymer-dispersed polyol (a) having stably dispersed polymer particulate in base polyol as, at least, a part of raw material of e.g. a two-pack type polyurethane-based coating film waterproof material or a moisture-curable one-pack type polyurethane-based coating film waterproof material. The polymer particulate is preferably one kind selected from acrylonitrile homopolymer, styrene homopolymer and acrylonitrile/styrene copolymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a waterproof material used for building materials and the like, and more specifically, a polyurethane waterproof film which cures at room temperature and has excellent physical properties after coating, and a coating using the same. Membrane waterproofing method.

[0002]

2. Description of the Related Art A two-part type room temperature curable composition comprising a base compound containing an isocyanate group-terminated polyurethane prepolymer as a main component and a curing agent containing an active hydrogen compound as a main component, or an isocyanate group-terminated polyurethane prepolymer. Polyurethane elastomers such as one-component moisture-curable compositions, which are the main components, have excellent waterproofness due to their excellent flexibility.
It is used for a wide range of building materials such as flooring materials, sealing materials, and elastic paving materials. In particular, it shows excellent waterproof and mechanical properties as a coating film waterproof material.

Among the above-mentioned two-part type room temperature curable compositions, an isocyanate group-terminated polyurethane prepolymer having an isocyanate group content of 2.5 to 4% by mass, which is obtained by a reaction of polyoxypropylene polyol and tolylene diisocyanate, is used. Polymer-based main agent, polyoxypropylene polyol and / or 4,4'-
The type consisting of a curing agent containing methylenebis (2-chloroaniline) as the main component is still the mainstream.

[0004]

A waterproof material or the like requires appropriate viscosity and thixotropy in view of workability during coating.
However, the above-mentioned 4, which is the mainstream as a two-pack type curing agent,
Since 4'-methylenebis (2-chloroaniline) is solid at room temperature, it is usually used by dissolving it in polyoxypropylene polyol at a concentration of 30 to 50% by mass. This mixed liquid has a high viscosity, and since a filler such as calcium carbonate is further mixed as a curing agent, the curing agent has a very high viscosity and the workability is deteriorated. Therefore, the solvent is added in an amount of 1 to 8% by mass for the purpose of reducing the viscosity to an appropriate level.

Also in the one-pack type, the isocyanate group-terminated polyurethane prepolymer as the main component has a relatively high viscosity, and since a large amount of a filler such as calcium carbonate is mixed in order to impart thixotropy, it is blended. It was necessary to add 3 to 20% by mass of a solvent in order to adjust the viscosity of the liquid. However, the use of a solvent is not preferable in terms of environmental hygiene, and the cured coating film may become thin due to the effect of solvent evaporation, and a stable coating film thickness may not be secured.

On the other hand, it is conceivable to use a large amount of plasticizer, but the use of an excessive amount of plasticizer tends to deteriorate the mechanical properties of the cured coating film, and particularly causes a decrease in tensile strength, tear strength and hardness. In addition, the adhesiveness with the top coat material such as the top coat is significantly deteriorated.

In order to maintain the mechanical properties of the coating film, in the case of the two-pack type, the isocyanate group content of the isocyanate group-terminated polyurethane prepolymer as the main component is increased to 4% by mass or more to obtain 4,4 'of the curing agent component. -It is also conceivable to increase the amount of methylenebis (2-chloroaniline) or the like. However, this method improves mechanical strength, but shortens the pot life and makes it easier for the cured coating film to foam during construction at high temperatures. The appearance of the coating film tends to be insufficient. On the other hand, when the isocyanate group content of the isocyanate group-terminated polyurethane prepolymer is similarly increased even in the one-component type, the cured coating film is likely to foam at room temperature, and the appearance tends to be poor. That is, there has been no polyurethane-based coating film waterproofing material having a moderately low viscosity of the curable composition and excellent mechanical properties of the cured coating film without using a solvent.

Therefore, an object of the present invention is to provide a polyurethane-based coating which has good workability during coating and good appearance of the coating after curing, and which does not deteriorate the mechanical properties of the cured coating even when a large amount of plasticizer is used. It is to provide a membrane waterproofing material.

[0009]

In order to achieve the above object, the polyurethane coating waterproof material of the present invention comprises a polymer dispersion in which polymer fine particles are stably dispersed in a base polyol as at least a part of a raw material polyol. It is characterized in that the polyol (a) is used.

According to the present invention, by dispersing the polymer fine particles, a highly rigid resin filler is dispersed in the polyurethane resin, and a polyurethane elastomer having high hardness and high modulus can be obtained. The mechanical strength of the waterproof material can be improved.
Moreover, since the initial curing time is shortened, the time during which walking is possible can be shortened. Further, the defoaming effect of the polymer fine particles promotes defoaming in and on the surface of the cured coating film, resulting in a good coating film appearance.

In a preferred embodiment of the present invention, the polymer fine particles dispersed in the polymer-dispersed polyol (a) is one selected from acrylonitrile homopolymer, styrene homopolymer and acrylonitrile / styrene copolymer. . According to this aspect, the rigidity of the polymer fine particles is remarkably high and the affinity with the polyurethane resin is good, so that the strength of the cured coating film can be greatly improved.

[0012] In another preferred aspect of the present invention, the polyurethane coating waterproof material is a hand-painted type which cures at room temperature and is used as a waterproof material, a floor material or an anticorrosive material. According to this aspect, it is possible to provide a hand-painted type waterproof film having good workability, and therefore it is particularly preferably used as a waterproof material, a floor material or an anticorrosive material.

In another preferred embodiment of the present invention, the polyurethane coating waterproof material contains 2 to 25% by mass of a plasticizer with respect to the total amount of the polyurethane coating waterproof material, and Does not contain solvent. According to this aspect,
Since the polymer particles having high polarity are scattered to improve the adhesiveness, the adhesiveness with the primer or the top coat is not deteriorated even in the waterproof material containing a large amount of the plasticizer.

In another preferred embodiment of the present invention, aromatic polyamine and / or polyol (b)
A two-component polyurethane coating film waterproof material comprising a curing agent containing as a main component and a main component containing an isocyanate group terminated polyurethane prepolymer as a main component obtained by reacting a polyisocyanate and a polyol (c). At least one of the polyol (b) and the polyol (c) contains the polymer-dispersed polyol (a).
According to this aspect, the mechanical strength of the obtained cured coating film, particularly the tensile strength, the tear strength, and the wear resistance can be greatly improved.

In another preferred embodiment of the present invention, the aromatic polyamine used in the curing agent is 4,
4'-methylenebis (2-chloroaniline), 4,4 '
-At least one selected from methylenebis (3-chloro-2,6-diethylaniline), bis (methylthio) toluenediamine, and diethyltoluenediamine. According to this aspect, it is possible to provide a polyurethane-based coating film waterproofing material that is cured at room temperature and has excellent mechanical strength of the obtained coating film.

As another preferred embodiment of the present invention, a moisture-curable one-component polyurethane-based coating containing an isocyanate group-terminated polyurethane prepolymer obtained by reacting a polyol (d) with a polyisocyanate as a main component. A membrane waterproofing material, wherein the polyol (d) contains the polymer-dispersed polyol (a). According to this aspect, the mechanical strength of the obtained coating film can be greatly improved.

In another preferred embodiment of the present invention, the polyisocyanate is tolylene diisocyanate or 4,4'-diphenylmethane diisocyanate. According to this aspect, it is possible to provide a polyurethane coating film waterproof material having excellent mechanical strength and elongation performance of the obtained cured product.

Further, the coating film waterproofing method of the present invention is a coating film waterproofing method using any one of the above polyurethane-based coating film waterproofing materials.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION First, the polymer-dispersed polyol (a) in the polyurethane coating waterproof material of the present invention will be described. The polymer-dispersed polyol (a) in the present invention is a dispersion system in which polymer particles (dispersoid) are stably dispersed in a base polyol (dispersion medium).
Examples of the polymer of the polymer particles include addition polymerization type polymers or condensation polymerization type polymers. The addition-polymerization polymer is obtained, for example, by homopolymerization or copolymerization of monomers such as acrylonitrile, styrene, methacrylic acid ester, and acrylic acid ester. Further, as the polycondensation polymer, polyester, polyurea,
Examples include polyurethane and melamine.

Of the above-mentioned polymers, the effect of improving the rigidity of the polymer fine particles is well exhibited, the effect of improving the hardness of the cured coating film is remarkable, and the curing speed is also high. Therefore, acrylonitrile homopolymer, styrene homopolymer, acrylonitrile / It is preferable to use one selected from styrene copolymers.

The polymer-dispersed polyol (a) can be produced by polymerizing a monomer in a base polyol, mixing polymer fine particles produced in a separate step with the base polyol, and a macromonomer having an ethylenically unsaturated bond. Examples thereof include a method of polymerizing an ethylenic monomer in a base polyol.

From the viewpoint of dispersibility and viscosity of the polymer particles, the content of the polymer particles is preferably 10 to 40% by mass based on the whole polymer-dispersed polyol (a), and 20
˜35% by mass is more preferred. In addition, the viscosity of the polymer-dispersed polyol (a) is preferably 2000 to 6000 mPa · s, and preferably 3000 to 5000 mPa, from the viewpoint of easy handling during production of the polyurethane-based coating film waterproof material and the product viscosity of the polyurethane-based coating film waterproof material.・ S is more preferable.

The above base polyol has 2 to 4 functional groups.
Those obtained by reacting the above initiator with propylene oxide alone or with propylene oxide and ethylene oxide in combination are preferable. When propylene oxide and ethylene oxide are used in combination, a mixture of the two may be reacted, separately and sequentially, or a combination thereof. Especially by reacting ethylene oxide last,
Polyoxypropylene polyoxyethylene polyol having a part of the terminal hydroxyl groups as primary hydroxyl groups is preferable because the stability of the polymer fine particles is good. The content of the oxyethylene group based on the finally reacted ethylene oxide is preferably 2 to 30% by mass with respect to the base polyol,
20 mass% is more preferable.

The base polyol has a hydroxyl value of 24 to
It is preferably 120 mgKOH / g of polyoxyalkylene polyol, more preferably a hydroxyl value of 30.
~ 60 mg KOH / g. Hydroxyl value is 24 mg KO
If it is less than H / g, the viscosity of the polyol becomes too high,
When it exceeds 0 mgKOH / g, it becomes difficult to use a necessary and sufficient blending part, which is not preferable. When calculating the hydroxyl value of the polymer-dispersed polyol, the mass of the polymer particles is included.

Next, the polyurethane resin in the polyurethane coating film waterproof material of the present invention will be described. In the case of a two-pack type polyurethane coating waterproof material, an isocyanate group-terminated polyurethane prepolymer obtained by reacting the polyol (c) and polyisocyanate is used.

As the polyisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate (hereinafter referred to as MDI), polyphenylene polymethylene polyisocyanate, carbodiimide-modified diphenylmethane diisocyanate (hereinafter referred to as carbodiimide-modified MDI) and the like are used. You can These may be used alone or in combination. Among the above, tolylene diisocyanate is most preferable from the viewpoints of viscosity, curability of the obtained isocyanate group-terminated polyurethane prepolymer and mechanical strength of the cured product, and particularly 2,4
-Tolylene diisocyanate with an isomer content of 80% by weight or more is preferred.

In the one-component moisture-curable polyurethane coating waterproof material, the isocyanate group-terminated polyurethane prepolymer obtained by reacting the polyol (d) with polyisocyanate is the main component, and the polyisocyanate is curable. From the viewpoint of mechanical strength, MDI is preferable.

The isocyanate group content of the isocyanate group-terminated polyurethane prepolymer is preferably 2.5 to 4 mass% for the two-pack type waterproof material and 4 to 6 mass% for the floor material. In addition, 0.2-
2.5 mass% is preferable.

Examples of the polyol (c) or (d) which is a raw material of the above isocyanate group-terminated polyurethane prepolymer include polyester polyol, polyether polyol, castor oil-based polyol, polybutadiene-based polyol and the like. Examples of the polyether polyol include polyoxypropylene polyol, polyoxypropyleneoxyethylene polyol, polyoxytetramethylene glycol and the like. The castor oil-based polyol is a castor oil or a modified polyol obtained by transesterifying castor oil with various alcohols and having different functional groups or molecular weights. Of the above polyols,
A polyether polyol is preferable for both the two-pack type and the one-pack type, and a polyoxypropylene polyol is particularly preferable.

The number of hydroxyl groups of the above polyol (c) or (d) is preferably 2 to 4, more preferably 2 to 3, particularly preferably 2 to 2.5, and most preferably 2.1 to 2.4.
Is. If the number of hydroxyl groups is less than 2, it becomes difficult to increase the molecular weight of the cured product, and the mechanical strength of the cured product becomes insufficient. If the number of hydroxyl groups exceeds 4, the crosslink density becomes too high and the elongation performance of the cured product deteriorates. Not preferable.

In the case of the two-pack type polyol (c), the hydroxyl value of the polyol is preferably 20 to 80 mgKOH / g, and particularly preferably 40 to 70 mgKOH / g. On the other hand, in the one-pack type polyol (d), 14 to 56 mg KO
H / g is preferred.

Next, the curing agent used in the two-pack type will be described. The curing agent for the two-component polyurethane waterproof film of the present invention contains an aromatic polyamine and / or a polyol (b) as a main component. Examples of the aromatic polyamine include 4,4'-methylenebis (2-chloroaniline), bismethylthiotoluenediamine, diethyltoluenediamine, 4,4'-methylenebis (3-chloro-2,6-).
Diethylaniline) and the like. Of these, 4,
Most preferred is 4'-methylenebis (2-chloroaniline). By using the above-mentioned aromatic polyamine, a cured coating film that is sufficiently cured at room temperature and has excellent mechanical strength due to the formation of urea bonds can be obtained. Further, by using the aromatic polyamine in combination with a polyol having a relatively high molecular weight, an appropriate elongation performance can be obtained.

The polyol (b) is preferably a polyoxypropylene polyol having 2 to 4 hydroxyl groups and a hydroxyl value of 10 to 112 mgKOH / g. When the number of hydroxyl groups is less than 2, it is difficult to make the cured coating film have a high molecular weight, so that the curability is deteriorated and the mechanical strength of the cured product becomes insufficient. When the number of hydroxyl groups exceeds 4, the crosslink density becomes too high and the elongation performance of the cured product deteriorates. Further, when the hydroxyl value is less than 10 mgKOH / g, the viscosity of the polyol becomes too high, resulting in 112 mgK
If it exceeds OH / g, the amount of the compounding agent in the curing agent is small because the molecular weight is small, and the amount of the plasticizer used instead is large, which is not preferable.

In the above-mentioned polyurethane resin, the mixing ratio of the main agent and the curing agent in the two-pack type is preferably 1 to 1.3 in terms of NCO ratio. However, the NCO ratio is a mixing ratio of an isocyanate group and an active hydrogen-containing group, that is, a molar ratio obtained by dividing the amount of the isocyanate group by the amount of the active hydrogen-containing group. Here, the active hydrogen-containing group, an amino group (-NH _2), a hydroxyl group (-OH) or the like, in the case of the polyol is a hydroxyl group. If the NCO ratio is less than 1, sufficient mechanical strength of the cured product may not be obtained, or tack may remain on the surface of the cured product, which is not preferable. On the other hand, if the NCO ratio exceeds 1.3, excess isocyanate groups are affected by moisture, and foaming tends to occur, or the cured product tends to become brittle, which is not preferable.

Next, a polyurethane coating film waterproof material using the polymer-dispersed polyol (a) as at least a part of the raw material polyol will be described. In the present invention, in the case of the two-component type, the polymer-dispersed polyol (a) may be contained in at least one of the curing agent polyol (b) and the main agent polyol (c).
In the case of the one-pack type, the polymer-dispersed polyol (a) is included in the polyol (d) which is reacted with the polyisocyanate. In particular, in the case of the two-component type, it is preferable to mix the polymer-dispersed polyol (a) with the curing agent polyol (b) from the viewpoint of workability.

The amount of the polymer-dispersed polyol (a) used depends on the content of the polymer solids such as acrylonitrile and styrene polymer in the polyol. 0.1-10 mass% is preferable with respect to the total polyurethane-based coating film waterproof material, and 0.5-5 mass% is especially preferable. If the polymer solids content is less than 0.1% by mass, the mechanical strength is insufficiently improved, and if it exceeds 10% by mass, the cured product becomes too hard and the elongation performance deteriorates.

Thus, by mixing the polyol with the polymer-dispersed polyol (a), the mechanical strength,
In particular, the tensile strength, tear strength and wear resistance can be greatly improved. Further, at the stage of initial curing, hardness develops quickly, and the time during which walking is possible can be shortened. Furthermore, the defoaming effect of the polymer fine particles promotes defoaming in and on the surface of the cured coating film, resulting in a good coating film appearance.

Even in a waterproof material containing a large amount of a plasticizer, the adhesion of the polymer particles such as acrylonitrile having a high polarity to the primer for the undercoat and the topcoat for the overcoat is greatly improved. It is possible to effectively prevent a decrease in adhesiveness due to

The polyurethane coating waterproof material of the present invention includes
A curing catalyst may be included to satisfy sufficient curability. As the curing catalyst, known catalysts that accelerate the urea / urethane reaction can be used, and examples thereof include organic acid lead, organic acid tin, and tertiary amine compounds.

In addition, additives such as fillers, pigments, stabilizers and plasticizers may be contained. Examples of the filler include calcium carbonate, talc, clay, silica, carbon and the like, and examples of the pigment include inorganic pigments such as chromium oxide and titanium oxide and organic pigments such as phthalocyanine pigments. Further, stabilizers such as antioxidants, ultraviolet absorbers and dehydrating agents which are generally used can be added to the polyurethane resin.

As the plasticizer, dioctyl phthalate, dibutyl phthalate, dinonyl phthalate, diisononyl phthalate, dioctyl adipate, chlorinated paraffin, petroleum plasticizer and the like can be used. In addition, bran oil fatty acid (analysis example:
Linoleic acid 33%, oleic acid 37%, palmitic acid 2
Mixture of 0%, 5% stearic acid and 5% linolenic acid), soybean oil fatty acid (analysis example: 44% linoleic acid, 32% oleic acid, 13% palmitic acid, 4 stearic acid)
%, Linolenic acid 7% mixture), rapeseed fatty acid (analysis example: linoleic acid 22%, oleic acid 58%, palmitic acid 5%, stearic acid 3%, and linolenic acid 12%) It is also possible to use a mixture of monocarboxylic acid methyl ester, which is a methanol ester of.

In this case, the content of the plasticizer is 2 to 25% by mass with respect to the total amount of the polyurethane coating film waterproof material, and it is preferable that substantially no solvent is contained.

The coating film waterproofing method of the present invention uses the above-mentioned polyurethane coating film waterproofing material of the present invention. The coating film waterproofing method of the present invention is suitable for waterproofing rooftops, balconies, balconies, open corridors, etc., because the resulting cured coating film has excellent mechanical properties.

[0044]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited thereto.
The following polyols were used as the polyols A to G used in each example. <Polyol used> Polyol A: Polyoxyalkylene triol having a hydroxyl value of 56.1 mgKOH / g, which is obtained by adding propylene oxide to glycerin. Polyol B: hydroxyl value obtained by adding propylene oxide to propylene glycol 56.1 mgKOH /
g of polyoxyalkylene diol. Polyol C: Polyoxyalkylene triol having a hydroxyl value of 28.1 mg KOH / g, which is obtained by adding propylene oxide to glycerin. Polyol D: hydroxyl value obtained by adding propylene oxide to propylene glycol 28.1 mgKOH /
g of polyoxyalkylene diol. Polyol E: Hydroxyl value 3 obtained by adding propylene oxide and ethylene oxide to glycerin in this order
Polyoxyalkylene triol having 4.3 mg KOH / g and an oxyethylene group content of 15% by mass. Polymer-dispersed polyol F: In 80 parts of polyol E,
Polymer-dispersed polyol having a hydroxyl value of 28.7 mg KOH / g obtained by radically polymerizing 20 parts of acrylonitrile. Polymer-dispersed polyol G: In 65 parts of polyol E,
Polymer-dispersed polyol having a hydroxyl value of 23.5 mg KOH / g obtained by radically polymerizing 27 parts of acrylonitrile and 8 parts of styrene.

Example 1 17 parts by mass of polyol A, 68 parts by mass of polyol B, and 15 parts by mass of tolylene diisocyanate (2,4-
80% by mass of isomer) (NCO ratio 2.03) was reacted to obtain a prepolymer having an isocyanate group content of 3.6% by mass, which was used as the main agent. 3.54 parts by mass of 4,4′-methylenebis (2-chloroaniline) and 8.29 parts by mass of polyol B are dissolved in a molten mixed solution, 10 parts by mass of polymer-dispersed polyol F, 14.16 parts by mass of dioctyl phthalate, A liquid obtained by mixing 60 parts by mass of calcium carbonate, 3 parts by mass of the pigment paste and 1 part by mass of lead 2-ethylhexanoate (lead content 24% by mass) was used as a curing agent.
The mixing ratio of the main agent and the curing agent is 1: 2 (NC
The two-component polyurethane coating film waterproof material of Example 1 was obtained with an O ratio of 1.07).

Example 2 The same prepolymer as in Example 1 was used as the main component. 4,4'-
3.55 parts by mass of methylenebis (2-chloroaniline),
In a molten mixed solution prepared by dissolving 10.92 parts by mass of polyol B, 6 parts by mass of polymer-dispersed polyol G, 15.53 parts by mass of bran oil fatty acid methyl ester, and 60 parts of calcium carbonate.
A liquid in which 3 parts by weight of the pigment paste, 3 parts by weight of the pigment paste, and 1 part by weight of lead 2-ethylhexanoate (lead content 24% by weight) were mixed was used as a curing agent. The mixing ratio of the main agent and the curing agent is 1: 2 (NCO is 1.07) in terms of mass ratio.
A two-component polyurethane coating film waterproof material was obtained.

Example 3 28.7 parts by weight of polyol C and 4 parts by weight of polymer-dispersed polyol G were reacted with 4 parts by weight of 4,4'-diphenylmethane diisocyanate (NCO ratio of 2.0) to obtain an isocyanate group terminal. 15 parts by mass of bran oil fatty acid methyl ester, 40 parts by mass of calcium carbonate, 5 parts by mass of magnesium hydroxide, 3 parts by mass of pigment paste, and bis (2-morpholinoethyl) ether in a prepolymer (isocyanate group content rate of 1.8% by mass) 0.3 parts by mass were mixed to obtain a one-component polyurethane coating film waterproof material of Example 3.

Comparative Example 1 The same prepolymer as in Example 1 was used as the main component. 4,4'-
3.55 parts by mass of methylenebis (2-chloroaniline),
In a molten mixed solution prepared by dissolving 8.29 parts by mass of polyol B, 10.23 parts by mass of polyol D, 13.93 parts by mass of dioctyl phthalate, 60 parts by mass of calcium carbonate, 3 parts by mass of pigment paste and lead 2-ethylhexanoate. A liquid obtained by mixing 1 part by mass (lead content 24% by mass) was used as a curing agent. Then, the mixing ratio of the main agent and the curing agent is 1: 2 by mass ratio.
A two-component polyurethane coating film waterproof material of Comparative Example 1 was obtained at a blending ratio (NCO ratio of 1.07).

Comparative Example 2 The same prepolymer as in Example 1 was used as the main component. 4,4'-
3.55 parts by mass of methylenebis (2-chloroaniline),
In a molten mixed solution obtained by dissolving 10.92 parts by mass of polyol B, 5 parts by mass of polyol C, 16.53 parts by mass of bran oil fatty acid methyl ester, 60 parts by mass of calcium carbonate, 3 parts by mass of pigment paste and lead 2-ethylhexanoate ( A liquid obtained by mixing 1 part by mass of a lead content of 24% by mass) was used as a curing agent. Then, the mixing ratio of the main agent and the curing agent is 1: 2 by mass ratio.
A two-component polyurethane coating film waterproof material of Comparative Example 2 was obtained at a compounding ratio of (NCO ratio of 1.07).

Comparative Example 3 32.7 parts by mass of polyol C and 4 parts by mass of 4,4′-
Diphenylmethane diisocyanate (NCO ratio of 1.9
6) is reacted with the isocyanate group-terminated prepolymer (isocyanate group content 1.79% by mass),
15 parts by mass of bran oil fatty acid methyl ester, 40 parts by mass of calcium carbonate, 5 parts of magnesium hydroxide, pigment paste 3
Part by mass and 0.3 part by mass of bis (2-morpholinoethyl) ether were mixed to obtain a one-pack type polyurethane coating film waterproof material of Comparative Example 3.

Test Example Each of the waterproof materials obtained in Examples 1 to 3 and Comparative Examples 1 to 3 was evaluated for curability, coating film physical properties and topcoat adhesiveness by the following methods. The results are summarized in Table 1. <Curability> Coating was performed on a slate plate at a coating amount of ² kg / m ² outdoors at 23 ° C. and a relative humidity of 50%, and the situation after 12 hours (determination of tack and walkability) was compared. ○ in the tack column in the table is non-sticky, Δ is slightly sticky, and × is highly sticky. In the table, "○" means that the person can walk sufficiently, "△" means that the footprint is thin, and "X" means that the footstep is clearly left. <Physical properties of coating film> The mechanical properties of the cured coating film were measured according to JIS-A6021. Ts in the table is tensile strength (unit:
N / mm ² ), Tr is the tear strength (unit: N / mm),
E indicates the elongation at break (unit:%). <Topcoat Adhesion> At 23 ° C and 50% relative humidity, a solvent-type acrylic urethane topcoat is applied 24 hours after applying the waterproof material (application amount 0.2 kg).
/ M ² ) and observed the adhesiveness after 24 hours. Using a razor, make 11 cuts on the surface of the top coat at 1 mm intervals vertically and horizontally to make a grid of 100 1 mm squares. After sticking cellophane tape on it, pull it vertically at a stretch. The number of squares left without peeling off the top coat when peeled off was expressed.

[0052]

[Table 1]

From the results shown in Table 1, in Examples 1 to 3 in which the polymer-dispersed polyol was used, the curability, the appearance of the coating film after curing and the mechanical properties were excellent, and Examples 2 and 3 containing a large amount of plasticizer It can be seen that the adhesiveness of the top coat is not deteriorated.

On the other hand, in Comparative Example 1, which is an example in which the polymer-dispersed polyol is removed from Example 1, the curability is inferior to that in Example 1. In addition, Examples 2 and 3
In Comparative Examples 2 and 3, which are examples in which the polymer-dispersed polyol is removed, the curability, the tensile strength, and the tear strength are decreased, and the adhesiveness to the top coat is also decreased as compared with the Examples due to the influence of the plasticizer. You can see that

[0055]

As described above, according to the present invention,
By using the polymer-dispersed polyol, it is possible to provide a polyurethane-based waterproof material that is excellent in curability, appearance of a coating film after curing, mechanical strength, and adhesiveness to a base or a top coat. This polyurethane coating film waterproof material is suitable for various uses such as a waterproof material, a floor material, and an anti-food material.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ identification code FI theme code (reference) B05D 7/24 302 B05D 7/24 302T C09D 175/04 C09D 175/04 201/00 201/00 (72) Inventor Ichiro Kamemura 23-Kawarai-cho, Kuki-shi, Saitama F-term (reference) within Asahi Glass Polyurethane Building Materials Co., Ltd. AA04 AA25 AA32 AA39 AB01 AB05 AB06 AC03 AC05 AE03 4J038 CC022 CC052 CG162 DG061 DG111 DG131 DG191 DG211 DG281 MA12 MA15 NA01 NA11 NA12 PB05

Claims (9)

[Claims] 1. A polyurethane coating waterproofing material, wherein a polymer-dispersed polyol (a) in which polymer fine particles are stably dispersed in a base polyol is used as at least a part of a raw material polyol. 2. The polymer fine particles dispersed in the polymer-dispersed polyol (a) is one selected from acrylonitrile homopolymer, styrene homopolymer, and acrylonitrile / styrene copolymer. Polyurethane coating film waterproof material. 3. The polyurethane-based coating film according to claim 1, wherein the polyurethane-based coating film waterproof material is a hand-painted type that cures at room temperature and is used as a waterproof material, a floor material, or an anticorrosive material. Waterproof material. 4. The polyurethane coating waterproof material contains 2 to 25% by mass of a plasticizer with respect to the total amount of the polyurethane coating waterproof material, and contains substantially no solvent.
The polyurethane-based coating film waterproof material according to any one of to 3. 5. A base compound containing an isocyanate group-terminated polyurethane prepolymer as a main component obtained by reacting a curing agent containing an aromatic polyamine and / or a polyol (b) as a main component with a polyisocyanate and a polyol (c). A two-component polyurethane coating film waterproof material comprising the following: wherein the polymer-dispersed polyol (a) is contained in at least one of the polyol (b) and the polyol (c). The polyurethane-based coating film waterproof material according to one. 6. The aromatic polyamine used in the curing agent is 4,4′-methylenebis (2-chloroaniline), 4,4′-methylenebis (3-chloro-2,6-).
The polyurethane coating film waterproof material according to claim 5, which is at least one selected from diethylaniline), bis (methylthio) toluenediamine, and diethyltoluenediamine. 7. A moisture-curable one-component type polyurethane coating waterproof material comprising an isocyanate group-terminated polyurethane prepolymer as a main component, which is obtained by reacting a polyol (d) with a polyisocyanate, the polyol comprising: The polyurethane coating waterproof material according to any one of claims 1 to 4, wherein the polymer-dispersed polyol (a) is contained in (d). 8. The polyurethane coating waterproof material according to claim 1, wherein the polyisocyanate is tolylene diisocyanate or 4,4′-diphenylmethane diisocyanate. 9. A coating film waterproofing method, which comprises using the polyurethane coating film waterproofing material according to any one of claims 1 to 8.