JP6799390B2 - High tensile product 2-component environmentally friendly urethane waterproof material composition for hand coating and urethane waterproofing method - Google Patents

Description

The present invention relates to a high-tensile two-component environment-friendly hand-coated urethane waterproof material composition and a urethane waterproofing method using the composition.

Urethane waterproofing material is suitable for construction of irregular shapes and narrow parts, so regardless of new construction or renovation work, flat areas such as balconies, balconies, open corridors, eaves, skirts, etc. Widely used for side grooves. On rooftops with a relatively large area, the so-called ventilation buffer method is often used, but it is common to use the close contact method for elevations, parapets, and pedestals. Further, on a concrete rooftop having a relatively small area, the close contact method is often used not only for the elevation, the parapet, and the pedestal, but also for the flat roof. In the ventilation buffer method, since the ventilation buffer sheet is installed between the base and the waterproof layer, cracks generated in the base concrete are shielded, and the crack followability of the urethane waterproof layer does not matter so much, but in the adhesion method, The crack followability of the urethane waterproof layer is an important factor for exhibiting sufficient waterproof performance.

In the adhesion method, a primer is applied to the base concrete, mortar surface, etc., and then a urethane waterproof layer is applied, and even if the urethane waterproof material is applied directly to the concrete base, adhesive strength cannot be obtained. In addition, since the primer partially penetrates into the concrete layer and hardens, it also has a certain degree of pinhole prevention effect and an effect of shielding moisture in the concrete. However, since the primer layer is a thin film of about 0.1 mm, if cracks occur in the underlying concrete, they will be destroyed almost at the same time. As a general rule, the primer and the urethane waterproof layer should be adhered to each other in principle, and if the adhesiveness is insufficient, the vapor pressure of moisture in the underlying concrete will increase due to the heat of sunlight after construction. Peeling and swelling may occur due to stress on the adhesive interface due to changes in the external environment such as a temperature difference from low temperature.
A solvent-based one-component moisture-curable urethane material is generally used as the primer, but the primer cannot completely shield the moisture in the underlying concrete. In addition, if there is an interval of 2 to 3 days or more between the application of the primer and the application of the waterproof layer, the adhesive strength with the urethane waterproof material will decrease, and even if it rains or condenses after applying the primer, It is also known that the adhesive strength with the urethane waterproof material is reduced, and it can be said that it is difficult to expect complete adhesion at the construction site.
In addition, the strength of the surface layer of concrete, which is the base, becomes very weak when the surface layer has a large amount of water or when the pressing is insufficient at the time of placing in a new construction. In the renovation, the existing concrete surface is weathered and has severe irregularities, so a latex mortar-based base conditioner is applied by about 1 mm, and a primer is applied on top of it to install a urethane waterproof layer. Since the treated material is not a material with high elongation and high strength, it will be destroyed at the same time as cracks occur in the underlying concrete.
When a hard and high-strength material such as urethane flooring is applied as a urethane waterproof layer on a roof exposed to sunlight, the fragile part of the underlying concrete layer and the primer due to the linear expansion and contraction force and hardening shrinkage force of the urethane flooring itself. There is an increased risk of peeling and swelling from parts with insufficient adhesive strength. In addition, high-strength materials such as urethane floor materials also increase costs. From the above, a general-purpose waterproof material is made of a material having relatively low strength and high elongation, and the low modulus suppresses the occurrence of peeling and swelling.

However, the current low-strength, high-stretchable waterproof material has low cohesiveness and is easily broken, so there is concern about its ability to follow the cracks in the base. Therefore, in principle, a reinforcing material such as glass mesh is used in the part where water leakage from the base crack is feared. By inserting a glass mesh, the strength becomes high and creep resistance (creep is a phenomenon in which strain increases with the passage of time when a continuous stress acts on an object) is also improved, so it is very effective when the crack width is small. It becomes. However, when the crack width is large, the glass mesh itself has no extensibility, so that the crack width is broken at about 2 mm, and the remaining coating film is weakened and easily broken, so it is never effective. It's not a method.
Furthermore, the work of inserting the glass mesh at the construction site is laborious and requires skill, and instead, inserting the glass mesh often causes construction defects such as deterioration of finish and occurrence of pinholes. , Insertion of glass mesh is also a cause of impairing the efficiency of urethane waterproofing material. On the other hand, the work of inserting the glass mesh has the advantage of ensuring the film thickness of the urethane waterproof material, and the safety of waterproofing is ensured in the part where the crack width is small, so this method is still the mainstream. ing.

Therefore, there are not many proposals for an efficient hand-painted urethane waterproofing method or urethane waterproofing material that does not use reinforcing materials such as glass mesh, but a relatively low-strength, high-stretch urethane waterproofing material is applied to the lower layer. However, a method of applying a urethane material having a relatively high hardness and high strength to the upper layer has been proposed (Patent Document 1). This method is an excellent method in which the urethane material in the upper layer is less likely to be broken because it is less likely to break or peel off from the underlying concrete layer and the urethane waterproof layer in the base reduces the movement of cracks. It is often used for special purposes such as parking lot floors. However, it is not efficient and economically worthwhile to bring in two types of materials and paint them separately in the construction of balconies, balconies, eaves, skirts, gutters, etc., which are the construction sites of general urethane waterproof materials. It is not widely adopted because it is not available.

As a test method for evaluating the crack followability and non-breakability of the waterproof material, the fatigue test (Non-Patent Document 1) or zero span specified in the JASS8 waterproofing work (hereinafter referred to as "JASS8") of the building work standard specification. Tension test can be mentioned.
When cracks occur in the underlying concrete, it is generally said that zero-span cracks occur, but in reality, the surface of concrete or mortar is composed of particles with a certain particle size, and the bonds between the particles are formed. Since is brittle, not a few minute ground fractures occur in the vicinity of crack occurrence, and strictly speaking, it is not a zero-span crack, so it can be said that a material with a high elongation rate is more effective for crack followability. Further, when a material having high hardness and high strength is applied, it is considered that the cohesive force of the coating film is high, so that the base fracture near the crack and the interfacial peeling occur relatively frequently.

Urethane waterproofing materials currently in use are classified into two types, high stretch type and high strength type, according to JIS A 6021 and building coating film waterproofing materials. The high-stretch type is a versatile waterproof material for hand coating, with an elongation rate at break (hereinafter referred to as "elongation rate") of 450% or more, and a tensile strength of 2.3 N / mm ² or more. The tensile product is specified to be 280 N / mm or more. On the other hand, the high-strength type is mainly made of ultra-fast-curing urethane material that is spray-applied by a dedicated spray device that collides and mixes two highly reactive components, with an elongation rate of 200% or more and a tensile strength of 10 N / It has a standard of mm ² or more and a tensile strength of 700 N / mm or more, and is often used for special purposes such as waterproof floors for parking lots, root-resistant waterproof materials for rooftop greening, and waterproof materials for metal roofs. ..
It should be noted that the tensile strength is indicated by (tensile strength x elongation) / 5, which has a barometer-like meaning of the fracture energy (tensile test) of the coating film, and is strong in order to increase the tensile strength. Not only that, it is necessary to increase the growth rate.

However, in general, in order to increase the strength of urethane waterproofing material, it is necessary to use a large amount of highly cohesive material, and by increasing the cohesiveness, the binding force increases, so the elongation rate decreases. It is customary. Even in the ultra-fast-curing urethane material to be spray-coated, it is relatively easy to increase the strength because many highly cohesive materials are used, but it is difficult to increase the elongation, and the material tends to be a hard material with a reduced elongation rate. As a result, it is used more as a floor material rather than as a waterproof material.
Highly elongate urethane waterproofing materials for hand coating, which are currently widely used, are mainly composed of an isocyanate group-terminated prepolymer composed of tolylene isocyanate (hereinafter referred to as "TDI") and a polyoxypropylene polyol. As a reaction component in the curing agent, 3,3'-dichloro-4,4'-diaminodiphenylmethane (hereinafter referred to as "MOCA"), which is a relatively low-reactivity aromatic polyamine, is the main component and is low. A polyoxypropylene polyol, which is a reactive and low-aggregation secondary polyol, is also used. In addition, lead carboxylate is generally used as an accelerator in order to promote the reaction of a low-reactivity polyoxypropylene polyol. In the absence of lead carboxylate, the reaction with water also proceeds, and carbon dioxide gas produced as a by-product causes a foaming phenomenon. The above-mentioned waterproof material is called a MOCA cross-linked waterproof material, and MOCA is a raw material having strong crystallinity and poor solubility, but it can be dissolved and stabilized to some extent in polyoxypropylene polyol, and the whole It is still used as a general-purpose waterproofing material because it has a mild reactivity and has a pot life suitable for hand-painting.

A general urethane waterproof material is obtained by mixing two liquids with a stirrer and then hand-painting with a trowel, spatula, roller, brush, etc. After mixing with a stirrer, the usable time is at least about 30 minutes. (Hereinafter, referred to as "potential time". The potable time is generally the time from after mixing the two liquids at 23 ° C. until the viscosity reaches 60,000 mPa · s.) It is said that. Since the outside temperature of the two-component urethane waterproofing material for hand coating differs greatly between winter construction and summer construction, a summer formulation suitable for construction at around 30 ° C in summer and construction at around 5 ° C in winter In general, a winter formulation suitable for the above is prepared, and it is devised so that the pot life is 30 minutes or more as much as possible at the construction temperature of each season.
In addition, it is desired that the urethane waterproof material is applied in the evening and then cured so that it can be lightly walked the next morning, and it is best that the curing time can be adjusted within 17 hours throughout the year.

In order to increase the strength of the MOCA crosslinked waterproofing material, it is necessary to increase the concentration of MOCA, which has high cohesiveness, and reduce the amount of polyol, which has low cohesiveness, but MOCA has no dissolving power, so it is limited. There is. Further, although there is a modified MOCA having improved solubility, the elongation rate is lowered because it is polyfunctionalized by the modification. Therefore, it is possible to increase the strength to some extent by increasing the NCO content of the main agent as in the urethane floor material, but the elongation rate decreases.

The MOCA crosslinked waterproof material has a big environmental problem. MOCA used as a curing agent is designated as a Class 2 Specified Chemical Substance by the Industrial Safety and Health Law, and since it is used in a curing agent in excess of 1% of the upper limit, obstacles such as Specified Chemical Substances, etc. It becomes a preventive rule (hereinafter referred to as "specialization rule") applicable product. MOCA is also classified into Group 1 (indicating carcinogenicity to humans) in the carcinogenicity evaluation by the IARC (International Agency for Research on Cancer).
In addition, the TDI used as the main agent is also designated as a specific chemical substance, and since the free TDI is present in the main agent of general-purpose products in excess of 1% of the upper limit, the main agent is also a product subject to the special rules. As a result, various restrictions are imposed during manufacturing and construction. Furthermore, the lead carboxylate compound used as an accelerator is a material whose use is strictly restricted worldwide, and is designated as a specified type 1 designated chemical substance under the Chemical Substance Emission Control Law (commonly known as the Chemical Substances Control Law). It is a material that should be avoided from the environmental point of view.

Further, a DETDA crosslinked urethane waterproofing material using diethyl toluenediamine (hereinafter referred to as "DETDA"), which is a highly reactive aromatic polyamine, has been developed instead of MOCA. This method has a problem in securing the pot life because DETDA is highly reactive, and a method using a main agent using a special TDI, a method using a special polyol as a curing agent, and the like have been proposed. .. (Patent Document 2)
Since DETDA has high cohesiveness, it is relatively easy to increase the strength by using a large amount of DETDA, but increasing the amount of DETDA further shortens the pot life, which worsens workability especially in summer. It ends up.
However, the DETDA crosslinked waterproofing material does not need to use a specialized material as a curing agent, and the free TDI content in the main agent can be 1% by mass or less (Patent Document 3), and lead carboxylate. Since it is not necessary to use the above, it is an environmentally superior waterproof material than the MOCA crosslinked type.
On the other hand, the ultrafast curing spray material uses diphenylmethane diisocyanate (hereinafter referred to as "MDI"), which is more reactive and more cohesive than TDI, as the main agent, and DETDA, which is also highly reactive as the curing agent. Is used, and gels in several tens of seconds after collision mixing and cures in several minutes.
From the viewpoint of raw materials, it is suitable for increasing the strength, but it is difficult to secure the elongation rate and reduce the modulus, so that it is often used as a flooring material.

In addition, for IPDI prepolymer using isophorone diisocyanate (hereinafter referred to as "IPDI") and a special polyol as the main agent, DETDA, water, and polyol are essential reaction components, and a small amount of a special plasticizer is used. The technology (Patent Document 4) of the non-bleed, high-strength, high-elongation hand-painted urethane waterproof material composition is also disclosed, but the physical properties are specified in the JIS standard (building coating waterproof material, JIS A 6021). A method of increasing the strength by heating at 60 ° C. is shown instead of the curing condition of 23 ° C., which is a waterproof material technology mainly for coating on asphalt-based substrates.

Japanese Unexamined Patent Publication No. 2000-7896 Japanese Patent No. 3114557 Japanese Unexamined Patent Publication No. 2013-139559 Japanese Unexamined Patent Publication No. 2014-227522

Architectural Institute of Japan, "Standard Specifications for Building Construction / Explanation JASS8" Reference Material 1 Performance Evaluation Test Method for Membrane Waterproof Layer 3.3 Fatigue Test (Type A) 2000 Revised (4th), p. 423-425

Until now, the relationship between the coating film performance of the urethane waterproof material alone and the crack followability has not been studied so much, and the solution has been to insert a reinforcing material such as glass mesh. However, this method is to insert a non-stretchable glass mesh into a highly stretchable urethane waterproof material, which is irrational, and if the crack width becomes slightly large, the glass mesh is easily broken and applied. It induces the breakage of the film.

In addition, it takes a lot of skill to insert the glass mesh properly at the construction site, and it is easy to induce defective parts such as pinholes and deterioration of finish, which is more rational in these days when there are few skilled technicians. A simple construction method and material are desired. In addition, sufficient studies have been made on what kind of composition of the waterproof material ensures practical workability, has excellent crack followability, and is unlikely to cause problems such as peeling and swelling after construction. Absent.

The present application is a fatigue test on the issue of what kind of coating film performance urethane waterproofing material ensures practical workability, has excellent crack followability, and is less likely to cause problems such as peeling and swelling after construction. Consideration was made by (JASS8) and zero span tension test. As a result, it was found that a urethane waterproof material having high stretchability and high tensile strength is suitable instead of a high-strength waterproof material. At the same time, we examined the composition of urethane waterproof material that satisfies the above performance, is excellent in actual workability, and has no problem in terms of environmental friendliness. As a result, a prepolymer containing isophorone diisocyanate and a polyoxyalkylene polyol is used as a main agent, and DETDA is contained in a two-component waterproofing material containing DETDA as a reaction component in a curing agent and a specific amount of plasticizer and filler. The ratio of the amino group equivalent of the aromatic polyamine to the amount of the plasticizer used was set within a specific range, and the isocyanate group of the main agent and the active hydrogen group of the curing agent were blended in a specific range to complete the process.

The present invention is a two-component hand-coated urethane composed of a main agent containing an isocyanate group-terminated prepolymer composed of a polyisocyanate and a polyol, and a curing agent containing an aromatic polyamine as a reaction component, a plasticizer and an inorganic filler. It is a waterproof material composition
The main agent polyisocyanate contains isophorone diisocyanate, the main agent polyol contains a polyoxyalkylene polyol, and the main agent polyol contains 20 to 97 equivalent% of diols having a molecular weight of 1500 or more, diols having a molecular weight of less than 1500, and 3 or more functional groups. The NCO content of the isocyanate group-terminated prepolymer is more than 2.3% by mass and 5.5% by mass or less.
The curing agent contains more than 80 equivalents of aromatic polyamines in the total reaction components, the aromatic polyamines containing diethyltoluenediamine, and 20-80% by mass of an inorganic filler.
The plasticizer is blended in the curing agent or in both the main agent and the curing agent so that the amount of the plasticizer is 16 to 80 parts by mass with respect to 100 parts by mass of the prepolymer in the main agent.
The ratio of the amount of amino groups (millimeter equivalent) to the amount of plasticizer (g) of the aromatic polyamine is 1.6 to 3.4.
It is characterized in that the equivalent ratio of the isocyanate group of the main agent to the amino group of the aromatic polyamine which is the reaction component in the curing agent is 0.9 to 1.4.

The present invention includes the following aspects.
[1] Two-component hand-painted urethane waterproofing consisting of a main agent containing an isocyanate group-terminated prepolymer composed of a polyisocyanate and a polyol, and a curing agent containing an aromatic polyamine as a reaction component, a plasticizer, and an inorganic filler. It is a material composition
The main agent polyisocyanate contains isophorone diisocyanate, the main agent polyol contains a polyoxyalkylene polyol, and the main agent polyol contains 20 to 97 equivalent% of diols having a molecular weight of 1500 or more, diols having a molecular weight of less than 1500, and 3 or more functional groups. 3 to 80% by weight of the polyols of the above are combined, and the NCO content of the isocyanate group-terminated prepolymer is more than 2.3% by mass to 5.5% by weight.
In the curing agent, 80 equivalent% or more of all the reaction components is aromatic polyamine, the aromatic polyamine contains diethyltoluenediamine, and 20 to 80% by mass of an inorganic filler is contained.
The plasticizer is blended in the curing agent or in both the main agent and the curing agent so that the amount of the plasticizer is 16 to 80 parts by mass with respect to 100 parts by mass of the prepolymer in the main agent.
The ratio of the amount of amino groups (millimeter equivalent) to the amount of plasticizer (g) of the aromatic polyamine is 1.6 to 3.4.
A two-component hand-coated urethane waterproof material composition in which the equivalent ratio of the isocyanate group of the main agent to the amino group of the aromatic polyamine which is the reaction component in the curing agent is 0.9 to 1.4.
[2] The two-component hand-painted urethane waterproofing material according to [1], wherein the ratio of the amount of amino groups (milli equivalent) to the amount of plasticizer (g) of the aromatic polyamine is 1.6 to 3.0. Composition.
[3] The two liquids according to [1] or [2], wherein the equivalent ratio of the isocyanate group of the main agent to the amino group of the aromatic polyamine which is the reaction component in the curing agent is 0.92 to 1.24. Urethane waterproof material composition for mold hand coating.
[4] The reaction accelerator is selected from the group consisting of an organic stannic compound, a metal carboxylic acid salt, a carboxylic acid, an acid anhydride and a tertiary amine in the main agent, the curing agent or the mixture of the main agent and the curing agent. The two-component hand-coated urethane waterproof material composition according to any one of [1] to [3], which comprises at least one of the above.
[5] The two-component hand according to any one of [1] to [4], wherein the organic stannic compound or the imidazole compound is blended in the main agent, the curing agent or the mixture of the main agent and the curing agent. Urethane waterproof material composition for coating.
[6] The two-component hand-coated urethane waterproof material composition according to any one of [1] to [5], wherein more than 70 equivalent% of polyisocyanate is isophorone diisocyanate.
[7] The two-component hand-coated urethane waterproof material composition according to any one of [1] to [6], wherein more than 50 equivalent% of the main agent polyol is a polyoxyalkylene polyol.
[8] The two-component hand-coated urethane waterproof material composition according to any one of [1] to [7], wherein more than 70 equivalent% of the aromatic polyamine is diethyltoluenediamine.
[9] The two-component hand-coated urethane waterproof material composition according to any one of [1] to [8], which has a tensile product of 600 N / mm or more.
[10] The two-component hand coating according to any one of [1] to [9] after the primer layer is applied to the adherend, or after the primer layer and the urethane waterproof material layer are applied. Urethane waterproofing method including the process of applying urethane waterproofing material composition.
[11] The two-component hand-coated urethane according to any one of [1] to [9] after applying a ventilation buffer sheet, a polymer sheet or a polymer coating material to the adherend. Urethane waterproofing method including the process of applying the waterproofing material composition.

The two-component hand-painted urethane waterproof material of the present invention is hard to break even without a reinforcing material such as a glass mesh, and exhibits excellent crack followability, and is hard to cause peeling and swelling after construction. Therefore, the construction can be greatly simplified as compared with the conventional case, and the efficiency of the construction can be improved.
In addition, it is excellent in practical workability, and it is also excellent in terms of environmental friendliness because it does not use raw materials that meet the special rules.

FIG. 1 is a plan view and a front view of a zero span tension test piece. FIG. 2 shows the test process of the JASS8 fatigue test.

As a result of various studies, it was found that the so-called high tensile strength waterproofing material, which has a high elongation rate and higher strength than the conventional waterproofing material, has excellent ground crack followability. A detailed study focusing on "elongation at break" and "breaking energy" in the zero span tension test revealed that the waterproof material has higher elongation and tensile strength than the conventional low-strength and high-stretchable waterproof material. It was confirmed that the "elongation at break" and "fracture energy" in the zero span tension test were greatly increased. Further, it was found that in the conventional method of inserting the glass mesh, the glass mesh is broken when the crack width is about 2 mm, and the "breaking energy" is also low. On the other hand, in a low-stretch / high-strength waterproof material with a low elongation rate even if it has high strength, the "breaking energy" becomes high and it becomes difficult to break, but peeling or a base is formed at the interface between the base slate plate and the waterproof material. It is presumed that the coating film tends to be broken and the coating film is likely to peel off and swell, which is a concern even in practical situations. In the zero span tension test, a tensile test was performed at a relatively low speed (0.5 mm / min) in consideration of the creep resistance of the polymer.

Next, an evaluation was performed in a fatigue test (type A) according to the "JASS8 T501 Membrane Waterproof Layer Performance Evaluation Test Method 3.3 Fatigue Test" (hereinafter referred to as "JASS8 Fatigue Test"). Stretchable / high tensile strength waterproofing materials give good results, but low stretching / high strength waterproofing materials tend to cause cracks in the coating film, peeling and base destruction at the adhesive interface. ..
In general, when trying to increase the strength of a urethane waterproof material, the elongation rate tends to decrease due to the restraint by the cohesive force. Therefore, if the tensile strength is set to 10 N / mm ² or more in order to correspond to the JIS high-strength waterproof material, the material tends to have a high risk of causing peeling and swelling of the coating film after construction. Peeling and swelling of the waterproof layer may not be a problem if it is small, but it tends to expand over time, and as a result, it becomes easy to tear or hinders walking, which impairs the reliability of the waterproof material. It ends up.

The surface of mortar or concrete will have high strength if there is sufficient filling pressure, but in the realization site, there are fragile parts due to insufficient filling pressure, and there is a gap between the application of the primer and the application of the waterproof material. Depending on the construction conditions, there are some parts where sufficient adhesive strength cannot be obtained. In addition, since the surface of mortar and concrete bases used in repair work has deteriorated due to weathering and neutralization, relatively low-strength base treatment materials (latex mortar type) may be applied or the bases may already be used. In some cases, relatively low-strength paint or dissimilar coating material is applied. In such a case, by applying a low-stretch, high-strength waterproof material, there is a high risk that interface peeling with the base material and destruction of the base material will occur.

On the other hand, in the conventional low-strength, high-stretch waterproof material, although it follows cracks to some extent, the "breaking energy" is small, so the method of inserting a reinforcing material such as non-stretchable glass mesh is generally adopted. Has been done. This method restrains the high extensibility, which is an advantage of urethane waterproofing material, but it is possible to secure the construction thickness of the waterproofing material at the construction site, and the restraint of the glass mesh can prevent the creep phenomenon, and it also resists external stress. It has the advantage of becoming stronger. However, since the adhesiveness between the urethane resin and the glass mesh is poor, the "breaking energy" is not high at all, and when the crack width becomes about 2 mm or more, it easily breaks.

The conventional low-strength, high-stretch waterproof material has an elongation rate of about 600%, a tensile strength of about 300 to 500 N / mm, and a tensile strength of 3 to 4 N / mm ² , while the high-strength type has a tensile strength of about 3 to 4 N / mm ² . Generally, the elongation rate is about 400%, the tensile strength is about 900 N / mm, and the tensile strength is about 12 N / mm ² . On the other hand, the waterproof material having excellent crack followability and less likely to be peeled or swelled at the realization site preferably has an elongation rate of 500% or more as in the conventional high-stretchable waterproof material, which is 600% or more. The tensile load is more preferably 600 N / mm or more, more preferably 700 N / mm or more, and further preferably 800 N / mm or more. The tensile strength is forcibly 10 N / mm ² or more and it is not preferable that, preferably less than 5~10N / mm ^2, more preferably 6~9N / mm ^2.

As described above, by increasing the tensile strength while maintaining the elongation rate, the "elongation at break" and "breaking energy" in the zero span tension test are greatly improved, and a reinforcing material such as glass mesh can be inserted. The range that can be constructed without construction can be expanded more than before, and labor saving and efficiency of construction can be achieved. Further, the average thickness of the coating film at the time of construction is preferably 1 mm or more, and even if the material has high elongation and high tensile strength, the effect cannot be sufficiently exhibited if the coating film thickness is small. Although it is more effective than the conventional method to apply the waterproof material only once, it is preferable to apply the waterproof material in two or more times in order to secure the average film thickness. Further, although the top coat is currently widely used, a top coat that is relatively soft and has a high elongation rate is preferable, and the crack followability of the urethane waterproof layer is less likely to be adversely affected. The waterproof material of the present application is effective in the adhesion method with an inorganic base, but it is also suitable for overlaying on the existing urethane waterproof layer in repair work etc. (often via a primer) Ventilation buffer sheet, high It can also be used on a molecular sheet or a polymer coating material. In addition, in the construction of the outside corners and inside corners and the parts where it is difficult to secure the coating thickness, by inserting a tape-shaped or strip-shaped reinforcing material, the safety of waterproofing can be improved without significantly impairing the workability. It can be increased, and reinforcing materials such as conventional glass mesh and polymer mesh can be partially used.

Next, a urethane material suitable for high elongation and high tensile strength was examined.
In general, it is customary to reduce the elongation rate by increasing the strength, so it is possible to increase the tensile strength while ensuring the elongation rate, and it is also excellent in actual workability and environmental aspects. However, it is a very difficult technique to complete a waterproof material without any problems.
In the conventional MOCA cross-linked waterproofing material, it is necessary to increase the concentration of MOCA in order to increase the strength, but the solubility of MOCA is limited, and a polyfunctional modified MOCA with improved solubility is used. And the growth rate is impaired. In addition, environmental problems remain. Further, in the conventional DETDA crosslinked waterproofing material mainly composed of TDI prepolymer, it is necessary to increase the concentration of DETDA in order to increase the strength, but in that case, the pot life is further shortened. It cannot be a waterproof material with good workability throughout the year.

As a result of various studies, it was found that the purpose was achieved by using IPDI as the main agent polyisocyanate and using DETDA, which is a highly reactive aromatic polyamine, as the reaction component of the curing agent. It was also found that IPDI is considerably less reactive than TDI, but reacts relatively quickly with DETDA, can secure the pot life required for construction, and can achieve high tensile strength.

(Main agent NCO content)
Regarding the main agent, the NCO content needs to be more than 2.3% by mass and 5.5% by mass or less, and preferably more than 3.0% by mass and 5.0% by mass or less. If the NCO content is 2.3% by mass, it is difficult to achieve high tensile strength, and if it exceeds 5.5% by mass, it is difficult to secure the elongation rate and the pot life required for construction.

(Polyisocyanate)
The present invention needs to include IPDI as a polyisocyanate, but some other polyisocyanates can be used in combination. As the isocyanate that can be used in combination, a mildly reactive aliphatic or alicyclic polyisocyanate is preferable, and hexamethylene diisocyanate, norbornene diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated xylylene diisocyanate are preferable. Examples thereof include nat, hydrogenated diphenylmethane diisocyanate, and hydrogenated tetramethylxylylene diisocyanate.
In addition, some aromatic polyisocyanates such as tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), and tetramethylxylylene diisocyanate can also be used, but tolylene diisocyanate is regulated by the Industrial Safety and Health Law. It is a specific chemical substance and is not preferable from the environmental point of view. On the other hand, derivatives with more than bifunctionality such as IPDI nurate form and TMP duct form have also been commercialized, but many cannot be used because they tend to constrain the elongation rate, and 2 to 30 equivalents in the total polyisocyanate component. It is preferable to use it in the range of%.

(Main agent polyol)
The polyol used as the main agent preferably contains more than 50 equivalent% polyoxyalkylene polyol, more preferably more than 70 equivalent%. When the polyoxyalkylene polyol is 50 equivalents or less, it becomes difficult to secure low viscosity and elongation rate having excellent workability. Further, as the polyol, it is necessary to use 20 to 97 equivalent% of a diol having a molecular weight of 1500 or more, and 3 to 80 equivalent% of a diol having a molecular weight of less than 1500 and a polyol having 3 or more functional groups in total.
If the amount of diol having a molecular weight of 1500 or more is less than 20 equivalent%, it becomes difficult to use it as a main agent having excellent elongation and low viscosity to secure a pot life, and a diol having a molecular weight of less than 1500 and a polyol having 3 or more functional groups are used. If a total of 3 equivalents or more is not used, the heat resistance and alkali resistance will be insufficient.

(Molecular weight and number of functional groups of the base polyol)
Among the polyoxyalkylene polyols, polyoxypropylene polyol and polyoxyethylene propylene polyol which are not crystalline, have low viscosity and are excellent in economy are preferable. There is also a method of using a polyester polyol having high cohesiveness for high strength, but since the polyester polyol has a high viscosity, the prepolymer also has a high viscosity, and when it is taken out from the can, when two liquids are mixed, and when it is applied. Workability deteriorates. A large amount of solvent is required to improve workability, but problems such as environmental pollution by the solvent and cracks and peeling due to shrinkage of the cured product due to solvent scattering after curing occur. Furthermore, it is recognized that common aliphatic polyester polyols have excellent weather resistance and heat resistance, but have problems with hydrolysis resistance, alkali resistance, and bacterial resistance. Not suitable for use. On the other hand, since the polyoxyalkylene polyol which is a polyether polyol has low cohesiveness, the prepolymer also has a relatively low viscosity, and it can be applied even if the amount of solvent is 5% or less, and it has hydrolysis resistance and alkali resistance. It has excellent bacterial resistance and exhibits performance suitable for urethane waterproofing materials.

Further, as the polyol of the main agent, it is necessary to use 20 equivalent% or more of a diol having a molecular weight of 1500 or more in order to secure the elongation rate, and more preferably 30 equivalent% or more. However, if only a diol having a molecular weight of 1500 or more is used, no fractional point can be formed in the cured product and the concentration of urethane bonds also decreases, which causes a decrease in strength development and curability, and further a decrease in final strength. In order to solve this problem, it is necessary to use 3 to 80 equivalent% of the diol having a molecular weight of 1500 or less or the polyol having 3 or more functional groups in total, and it is more preferable to use 5 to 60 equivalent%. By using a diol having a molecular weight of 1500 or less, the concentration of urethane bonds and urea bonds in the cured product becomes high, so that high tensile strength can be achieved without significantly impairing the elongation rate. Further, by using a polyol having 3 or more functional groups, branch points can be formed in the cured product, so that the strength development and curability can be improved, and the strength can be easily increased.

As the diol having a molecular weight of 1500 or more, a general polyoxyalkylene diol can be used, and it is preferable to use polyoxypropylene diol and polyoxyethylene propylene diol having low crystallinity and low viscosity. As the diol having a molecular weight of less than 1500, it is preferable to use a polyoxyalkylene diol having a molecular weight of 200 to 1200 and a short-chain polyol.
As the polyoxyalkylene diol, general polyoxypropylene diol and polyoxyethylene propylene diol, which also have low crystallinity and low viscosity, are more preferable, and the NCO content can be increased without increasing the viscosity of the main agent so much. It is possible to achieve high strength without impairing the elongation rate. A polyether polyol having a molecular weight of 200 to 800 using bispheno A as an initiator has a high cohesive force among the polyethers and is effective for increasing the strength, and thus can be used more preferably. Further, among polyester polyols, low crystalline fragrance having a molecular weight of 300 to 800 using a non-crystalline polyol such as 2-methyl-1,3-propanediol or 3-methyl-1,5-pentanediol. Group polyester polyols can be used because they have good alkali resistance and high cohesiveness. However, it is difficult to use in large quantities due to its high viscosity. In addition, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentane Short-chain diols having a molecular weight of 200 or less, such as diols, ethylene glycols, diethylene glycols, dipropylene glycols, and tripropylene glycols, can also be used, but as the amount used increases, the elongation rate tends to be constrained and high strength tends to be hindered. , Preferably less than 50 equivalent%.

As the polyol having 3 or more functional groups, a polyoxyalkylene polyol having a molecular weight of 1500 or more can be used, and general polyoxypropylene triol or polyoxyethylene propylene triol is preferable. Since a polyoxypropylene polyol or a polyoxyethylene propylene polyol having 4 or more functional groups tends to constrain the elongation rate, it can be used only in a small amount. Polyoxyalkylene triol having a molecular weight of 1500 or less can also be used, and polyoxypropylene triol or polyoxyethylene propylene triol is preferable, but since there is a strong tendency to constrain the elongation rate, a small amount can be used. Further, trifunctional polyols such as trimethylolpropane and glycerin, and tetrafunctional or higher functional polyols such as pentaerythritol and sorbitol also tend to constrain the elongation rate, and therefore can be used only in a small amount.

(Main agent NCO group / OH group equivalent ratio)
Next, the equivalent ratio of the NCO group of the isocyanate group-terminated prepolymer in the main agent to the OH group of the polyol (NCO group / OH group) is preferably 1.5 to 2.5, preferably 1.6 to 1.6. It is more preferably 2.3. If the (NCO group / OH group) is less than 1.5, the thickening of the main agent becomes severe, and if it exceeds 2.5, the free IPDI increases, which causes problems such as a decrease in elongation rate and shortening of pot life. It will be easier.

(Main agent synthesis method)
Although it is a method for synthesizing an isocyanate group-terminated prepolymer, it is preferable to use a catalyst because the reaction is difficult to accelerate simply by heating. A general urethanization catalyst can be used, but among them, an organic ferrous tin catalyst such as DBTDL or DOTDL is preferable, and the reaction can be efficiently promoted by adding a small amount such as 0.0001 to 0.1% by mass. The reaction temperature is preferably 60 ° C. to 100 ° C., and the reaction can be completed in about 2 to 6 hours. After the reaction is completed, it is preferable to inactivate the catalyst with phosphoric acid or the like.

(Active hydrogen in curing agent)
As the curing agent, in order to achieve high tensile strength, it is necessary that more than 80 equivalent% of the reaction component is an aromatic polyamine, and more than 90 equivalent% is preferable. Although polyol as a reaction component has an effect of ensuring elongation to some extent, it is less effective for high tensile strength because it has lower cohesiveness than aromatic polyamines.
Further, since the polyol has low reactivity with the isocyanate group of IPDI, it is difficult to react at room temperature without using a reaction accelerator, but a carboxylic acid such as lead carboxylate conventionally used as a reaction accelerator When a metal salt is used, the reaction with DETDA is also promoted, so that the pot life may be shortened. Further, more than 70 equivalent% of the aromatic polyamine is preferably DETDA, more preferably more than 80 equivalent%, and most preferably more than 90 equivalent%. When DETDA, which is non-crystalline and highly reactive, is 70 equivalent% or less, it becomes difficult to secure curability and high tensile strength due to good reactivity with IPDI.

Examples of the aromatic polyamine that can be used in combination with the curing agent include Cure Hard MED (4,4'-methylenebis (2-ethyl-6-methylaniline)) manufactured by Ihara Chemical Industry Co., Ltd., which has the same high reactivity as DETDA. Kayahard AA (4,4'-methylenebis (2-ethylaniline)) manufactured by Nippon Kayaku Co., Ltd., Kayabond C-300 (4,4'-methylenebis (2,6-diethylaniline)) manufactured by Nippon Kayaku Co., Ltd. ), Kayabond C-400 (4,4'-methylenebis (2,6-diiso-propylaniline)) manufactured by Nippon Kayaku Co., Ltd. and the like. In addition, although it is a low-reactivity aromatic polyamine, Albemarle's EtaCure 420 (4,4'-methylenebis (N-sec-butylaniline)), Albemarle's EtaCure 300 (dimethylthiotoluenediamine), etc. Can be used.

As the polyol used as a reaction component, a polyol having a molecular weight of less than 1500 is preferable, and 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1 , 6-Hexanediol, 3-methyl-1,5-pentanediol, ethylene glycol, diethylene glycol, dipropylene glycol, tripropylene glycol and other short-chain polyols, polyester polyols, polycarbonate polyols and other relatively highly cohesive polyols. Can be mentioned. Among them, the primary hydroxyl group polyol is more preferable because it has high reactivity and is unreacted and hardly remains. Among them, 1,3-propanediol, 1,4-butanediol, 3-methyl1,5-pentanediol, and molecular weight. 300-800 aromatic-containing polyester polyols are more preferred for higher strength.
The aromatic polyester polyol is preferably a liquid product using a low crystalline polyol such as Kuraray (manufactured by Kuraray Co., Ltd.).
Further, a polyol having a molecular weight of 1500 or more can also be used, and a polyoxypropylene polyol or a polyoxyethylene propylene polyol having a low viscosity can be used, but it is not preferable from the viewpoint of high tensile strength due to its low cohesiveness. ..

(Inorganic filler)
It is necessary to add 20% by mass to 80% by mass of an inorganic filler to the curing agent. Without the reinforcing effect of the inorganic filler, high tensile strength would be inefficient and would not be a practical waterproof material. If the amount of the inorganic filler is 20% by mass or less, the reinforcing effect is insufficient, and if it is 80% by mass or more, the workability is deteriorated due to thickening.

Further, in the present application, by blending a large amount of plasticizer on the curing agent side, a large amount of inorganic filler can be blended, and an economical waterproof material can be obtained. Calcium carbonate is preferable as the inorganic filler. Calcium carbonate has a high economic effect, and at the same time, it has good dispersibility during the production of the curing agent, and even if it is blended in a large amount, the viscosity is small, and it is easy to reduce the sedimentation property during storage of the curing agent. But there are few adverse effects. Calcium carbonate includes various types of calcium carbonate such as heavy calcium carbonate, light calcium carbonate, and surface-treated colloidal calcium carbonate. Any calcium carbonate can be used, and the surface-treated colloidal calcium carbonate has a thixophilic property. It can also be used as an elevational waterproofing material with the above. In addition, some inorganic fillers such as silica, kaolin, talc, bentonite, aluminum hydroxide, and barium hydroxide can be used. Since the above-mentioned inorganic filler contains adhering water, the amount of water in the curing agent is about 1000 ppm to 3000 ppm, and the adhering water gradually reacts with the excess isocyanate group after mixing the two liquids. It is presumed that it contributes to higher physical properties.

(Plasticizer)
Next, in order to have the pot life required for construction throughout the year and to ensure high extensibility and high tensile strength performance, 16 parts by mass of plasticizer is added to 100 parts by mass of prepolymer in the main agent. ~ 80 parts by mass is required, and more preferably 20 parts by mass to 70 parts by mass. When the amount of the plasticizer is 16 parts by mass or less, it becomes difficult to secure the pot life and the elongation rate, and when it is 80 parts by mass or more, it becomes difficult to increase the tensile strength. In principle, the plasticizer is added to the curing agent, but it is also possible to add a part of the plasticizer to the main agent side.

As the plasticizer, a plasticizer that can be generally blended with urethane resin can be used. For example, phthalates such as diisononyl phthalate (DINP), dioctyl phthalate (DOP), butyl benzyl phthalate (BBP), aliphatic dibasic acid esters, phosphoric acid esters, trimellitic acid esters, sebacic acid esters , Epoxy fatty acid esters, glycol esters, animal and vegetable oil-based fatty acid esters, petroleum / mineral oil-based plasticizers, alkylene oxide polymerization-based plasticizers, and the like.
Among them, diisononyl phthalate (DINP) and diisononyl phthalate (DOP), which have a flash point of 200 ° C. or higher, are less likely to cause weight loss even in the long term, and are aromatic polyesters, which are less likely to cause hydrolysis. it can. Although a solvent can be used in the curing agent, there is a risk of shrinkage due to volatilization after construction, the inorganic filler tends to settle easily, and there is an environmental problem, so 5% by mass. It is preferably used within, and more preferably not used.

(Amino acid equivalent per plasticizer)
At the same time, it is important that the ratio of the amino group amount (milli equivalent) to the plasticizer amount (g) of the aromatic polyamine, the amino group (milli equivalent) / plastic agent (g), in the state where the main agent and the curing agent are mixed. (Hereinafter, also referred to as “amino group equivalent per plastic agent”) needs to be in the range of 1.6 to 3.4, and more preferably 1.6 to 3.0. If the "amino group equivalent per plasticizer" is less than 1.6, the concentration of aromatic polyamines becomes low and it is difficult to achieve high tensile strength, and if it exceeds 3.4, the pot life and the elongation rate can be secured. It gets harder. In order to achieve high tensile strength while ensuring the elongation rate, the role of the polyol as a reaction component is not so important, and the amount of plasticizer used and the "amino group equivalent per plasticizer" play important roles. Fulfill.

(Isocyanate group / aromatic amino group equivalent ratio)
Further, in the conventional DETDA crosslinked waterproofing material using TDI as the main agent, the equivalent ratio of the isocyanate group of the main agent to the aromatic amino group of DETDA (isocyanate group / aromatic) is used in order to prolong the pot life as much as possible. It is common practice to add a small amount of DETDA so that the amount of the amino group) is about 1.2 to 1.5 to make the NCO group excessive. In such a case, the excess NCO group remaining without reacting with DETDA is the water adhering to the inorganic filler blended in the curing agent, the water taken in from the air when the two liquids are mixed, and further. After coating, it gently reacts with water (moisture) absorbed from the surface of the coating film and self-crosslinks, and after a few days, the cured product has a higher molecular weight and higher strength. Further, even if the NCO group is excessive as described above, since the reactivity between the isocyanate group and DETDA is high, it exhibits relatively quick curing and can be cured the next day even at a low temperature. In JIS A 6021 (waterproof coating material for construction), it is stipulated that the physical properties of the waterproof coating material should be measured after 7 days under the standard condition of 23 ± 2 ° C. and 50 ± 10% humidity. However, in the conventional MOCA cross-linked waterproofing material and DETDA cross-linked waterproofing material using TDI prepolymer as the main component, self-crosslinking due to the reaction between the excess isocyanate group and water is almost completed in the curing period of 7 days. It has almost reached the maximum strength. Therefore, it is common to measure physical properties immediately after curing for 7 days under standard conditions.

On the other hand, in the DETDA crosslinked waterproofing material using the IPDI prepolymer of the present application as the main component, the curing process is significantly different from the conventional one, and the equivalent of the isocyanate group of the main agent and the amino group of the aromatic polyamine which is the reaction component in the curing agent. When the ratio (hereinafter, also referred to as “isocyanate group / aromatic amino group equivalent ratio”) is increased, the reactivity between the isocyanate group of excess IPDI and water is low, so that curability and strength development are exhibited. It was found that the final strength tended to be slower and the final strength tended to decrease, and the strength development was improved and the maximum strength was reached when the isocyanate group / aromatic amino group equivalent ratio was 1.0 to 1.1. As a result of further studies, it was found that the strength development and the final strength were improved to some extent by using the moisture curing accelerator. This effect becomes remarkable when the isocyanate group / aromatic amino group equivalent ratio exceeds 1.1, and at the same time, the physical properties after 14 days tend to be higher than the physical properties after 7 days under standard conditions. It is presumed that this is due to the progress of moisture hardening.

In addition, even when the isocyanate group / aromatic amino group equivalent ratio is increased by the combined use of polyol or water, the moisture curing accelerator also promotes the reaction with the polyol, thus increasing the strength development and final strength. It turned out. As a result, it is possible to obtain a waterproof material that is practical even if the isocyanate group / aromatic amino group equivalent ratio is around 1.3 as in the conventional waterproof material. When the isocyanate group / aromatic amino group equivalent ratio is designed to be about 1.0, a slight deviation in the compounding ratio at the construction site (especially when used in small portions) causes an excess of amino groups. The probability is high, and curing defects are likely to occur. In the conventional waterproof material using TDI, the foaming property may become severe when a moisture curing accelerating catalyst is used, but in the case of the main agent using IPDI, the reaction with water is gentle, so that Such a phenomenon is unlikely to occur.

Next, further studies were conducted on polyols and water as reaction components to be blended in the curing agent. When a polyol is used, a polymer polyol having a molecular weight of 1500 or more has relatively low cohesiveness and is not suitable for high tensile strength, and a polyol having a molecular weight of less than 1500 and having a relatively low molecular weight is preferable. Further, a primary polyol having high reactivity is preferable to a secondary polyol having low reactivity such as polyoxypropylene polyol. Similar to polyols, water contributes less to high tensile strength and has low reactivity with IPDI prepolymers. In addition, when water or a polyol is used in combination, the reaction accelerator is an organic bistin compound or the 1st position rather than the conventionally used carboxylic acid metal salt such as lead carboxylate, as in the case of promoting moisture curing described above. It is preferable to use an imidazole compound having a substituent at the 2-position, and the reaction can be promoted without shortening the pot life. Some polyols and water can be used in combination to adjust the workability such as pot life and curing time, and to adjust the performance such as elongation and strength, but for high tensile strength, isocyanate group / The aromatic amino group equivalent ratio should not exceed 1.4.

From the above, in the present application, the curing condition of 7 days in the conventional standard state is extended to 14 days in some cases, and in some cases, by using a moisture curing accelerating catalyst, the isocyanate group / aromatic amino group equivalent ratio Can be carried out in a wide range of 0.9 to 1.4. If the isocyanate group / aromatic amino group equivalent ratio exceeds 1.4, high tensile strength becomes difficult, and if it is 0.9 or less, the number of terminal amino groups increases during the curing process and the physical properties deteriorate. Furthermore, since the amount and concentration of aromatic amino groups are important for high tensile strength, the isocyanate group / aromatic amino group equivalent ratio is preferably 0.92 to 1.30, and further. More preferably, it is 0.95 to 1.24.

(Curing accelerator)
In the present application, an organic stannic compound, a tertiary amine, a carboxylic acid metal salt and the like, which are said to have an effect of promoting moisture curing in the reaction with an isocyanate group, can be used as a reaction accelerator.
Examples of the organic ditin-based compound include dibutyltin oxide, dioctyltin oxide, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin di2-ethylhexanoate, dioctyltin diacetate, dioctyltin dilaurate, dibutyltin dimercaptide, and dibutyl. Examples thereof include tin bisacetylacetonate, dibutyltin oxylaurate, dioctyltin dineodecanate, dibutyltin bisbutylmalate and dioctyltin2-ethylhexylmalate, and among them, dibutyltin dilaurate and dioctyltin dilaurate are preferable. It is preferable to use 0.001 to 0.1% by mass of the organic stannic compound in the curing agent.

As the tertiary amine, for example, general tertiary amines such as triethylamine, tributylamine, triethylenediamine, N-ethylmorpholine, bis (2-morpholinoethyl) ether, and diazabicycloundecene can be used. An imidazole compound, which is a special tertiary amine, is preferable from the viewpoint of suppressing foaming and promoting high-intensity expression, and examples of the imidazole compound include 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, and 1-benzyl-. Compounds having substituents at the 1- and 2-positions such as 2-methylimidazole and 1-benzyl-2-phenylimidazole, and compounds having a substituent at the 1-position such as 1-methylimidazole and 1-allyl imidazole Can be used. Among them, the imidazole compound having a substituent at the 1-position and the 2-position has a high strength expression promoting effect and is more preferable. The tertiary amine is preferably used in an amount of 0.01 to 2.0% by mass in the curing agent.

In general, a carboxylic acid metal salt which is a urethanization catalyst can also be used. Although the carboxylic acid metal salt has a weak effect of promoting moisture curing, it strongly promotes the reaction with aromatic polyamines and shortens the pot life and curing time. Therefore, it is preferable to use it as a catalyst for winter rather than a catalyst for summer. Examples of the carboxylic acid metal salt include 2-ethylhexanoic acid, neodecanoic acid, naphthenic acid, oleic acid, linoleic acid, linolenic acid, lead salt of resin acid, zinc salt, bismuth salt, zirzyl zyl salt, tin salt and copper salt. , Magnesium salt, calcium salt, strontium salt, barium salt and the like. Among them, calcium 2-ethylhexanoate and zinc 2-ethylhexanoate are preferable because they have a high effect of promoting high strength expression. The carboxylic acid metal salt is preferably used in an amount of 0.1 to 4.0% by mass in the curing agent. On the other hand, lead carboxylate has a high effect of shortening the pot life and the curing time, but the effect of promoting the development of high strength is not so much observed, and it is not preferable to use it from an environmental point of view.

As described above, compounds that are thought to promote moisture curing can be used, but among them, organic stannic compounds and imidazole compounds promote high strength without shortening the pot life. It is also excellent in foaming inhibitory property, and can be particularly preferably used as a catalyst for summer.
Further, the imidazole compound is more preferable because it has a strong tendency to promote thermal deterioration when a large amount of metal-based catalyst is added, whereas it has a feature that it hardly promotes thermal deterioration even when it is added in a large amount. In principle, the moisture curing accelerator is added to the curing agent, but a considerable amount may be added at the construction site when the two liquids are mixed. On the other hand, although it is possible to add it to the main agent side, it is not so preferable because it may impair the storage stability.

On the other hand, carboxylic acid or acid anhydride promotes the reaction between the IPDI prepolymer and the aromatic polyamine, so that it is effective in shortening the pot life and curing time, and it also promotes thermal deterioration like a carboxylic acid metal salt. Therefore, it can be particularly preferably used as a winter accelerator. However, since there is almost no effect of promoting moisture curing, a high strength development promoting effect cannot be expected so much in a formulation having a high isocyanate group / aromatic amino group equivalent ratio.
Examples of the carboxylic acid include propionic acid, 2-methylpentanoic acid, octyl acid, isononanoic acid, naphthenic acid and the like, and octyl acid is preferable.
Examples of the acid anhydride include phthalic anhydride, hexahydrophthalic anhydride, methyl-hexahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, among which methyl-tetrahydrophthalic anhydride is used. preferable.
It is desirable to use 0.05 to 2.0% by mass of the carboxylic acid and the acid anhydride in the curing agent, and a part or the whole amount thereof may be blended on the main agent side.

Furthermore, a detailed study of an acid anhydride catalyst that promotes the reaction between the IPDI prepolymer and the aromatic polyamine revealed that when it was added to the curing agent as in the conventional catalyst, the amino groups, hydroxyl groups, and the like in the curing agent It is thought that it is added to active hydrogen such as water to generate a carboxylic acid group, and it is an accelerator that promotes curing but at the same time shortens the pot life. However, when blended on the main agent side, the acid anhydride can be maintained in a stable state without being added to active hydrogen, and when mixed with the curing agent, it is added to amino groups, hydroxyl groups, water, etc. in the curing agent. It is considered that it generates a carboxylic acid group and exerts a promoting effect. At that time, probably because the addition reaction with amino groups, hydroxyl groups, water, etc. requires a certain amount of time, it is possible to take a longer pot life when it is added to the main agent side than when it is added to the curing agent side. Moreover, the curability can be made equivalent. As a result, it has been found that it is very preferable as a urethane waterproof material because it can exert an effect as an ideal latent catalyst. It was also found that the same potential was exhibited by adding an acid anhydride when mixing the main agent and the curing agent at the construction site. Therefore, in the present application, it is preferable to mix the acid anhydride on the main agent side in advance, or to add the acid anhydride when the main agent and the curing agent are mixed. However, the method of adding acid anhydride at each construction site has problems such as storage stability and management of acid anhydride, and measurement error due to complexity at the construction site. A method of blending in advance on the main agent side is more preferable.

(Other additives)
In addition, additives such as a wetting agent, a defoaming agent, a pigment, and a weather resistance imparting agent can be added to the curing agent, if necessary.

(Main agent / curing agent compounding ratio)
The blending ratio of the main agent and the curing agent is not particularly limited, but is preferably in the range of 1/1 to 1/2 in terms of mass ratio. However, in general, when 1/2 is blended, the amount of plasticizer increases, which is disadvantageous for high tensile strength. Therefore, it is preferably less than 1/1 to 1/2, and 1 to 1 to 3. More preferably, it is / 4.

(Waterproof method)
Further, the high tensile strength urethane waterproof material of the present application cannot be directly applied to an inorganic base such as concrete. In the case of an inorganic base, it does not adhere to the urethane waterproof material, so it can be applied after applying a primer that can shield the base water to some extent and ensure adhesiveness. In some cases, an intermediary primer can be applied on the existing urethane waterproof layer, including during repairs. Further, it can be applied after fixing a polymer sheet such as a ventilation buffer sheet or a vinyl chloride sheet, a rubber sheet, or a non-woven fabric sheet to an inorganic base with a primer, an adhesive, mechanical fixing, a laying or the like. Further, even in the case of a metal-based substrate, since the adhesiveness cannot be ensured even if the high-strength urethane waterproof material of the present application is directly applied, it can be applied after applying a special primer.
The present invention does not aim at repairing an asphalt-based waterproof layer, but aims at waterproofing and protecting an inorganic base such as concrete, a metal-based base, a polymer-based resin base, and a rubber base. Further, in principle, the high-strength urethane waterproof material of the present application is to be coated with a top coat when it is used in a part exposed to direct sunlight.

Raw materials The raw materials used in the following examples and comparative examples are as follows.
[Isocyanate]
IPDI: VESTANAT® IPDI, isophorone diisocyanate alone, NCO content 37.8% by mass, NCO functional group number about 2.0, Ebonic Japan Co., Ltd. T-80: Coronate T-80, 2, 4 -Trirange isocyanate / 2,6-Trirange isocyanate = 80/20 (mass ratio) mixture, NCO content 48.3% by mass, manufactured by Toso Co., Ltd. T-100: Coronate T-100, 2,4 − Trilenid isocyanate 100% content, NCO content 48.3% by mass, manufactured by Toso Co., Ltd. MDI: Millionate MT, 4,4'-diphenylmethane diisocyanate, NCO content 33.6% by mass, Nippon Polyurethane Industry Made by Co., Ltd. [Polycarbonate]
Sanniks PP-2000: Polyoxypropylene diol, average molecular weight 2000, OH value 56.1 mgKOH / g, Sanyo Kasei Kogyo Co., Ltd. Sanniks GH-3000: Polyoxypropylene triol, average molecular weight 3000, OH value: 56.1 mgKOH / G, Sanyo Kasei Kogyo Co., Ltd. Sanniks GH-5000: Polyoxypropylene triol, average molecular weight 5000, OH value: 33.7 mgKOH / g, Sanyo Kasei Kogyo Co., Ltd. New Pole BP-5P: Polyoxypropylene diol, Average molecular weight 500, OH value: 209 mgKOH / g, Sanyo Kasei Kogyo Co., Ltd. Sanniks PP-400: Polyoxypropylene diol, average molecular weight 400, OH value 280.5 mgKOH / g, Sanyo Kasei Kogyo Co., Ltd. Clare polyol P- 530: Aromatic polyesterdiol obtained by the reaction of 3-methyl-1,5-pentanediol with isophthalic acid, average molecular weight 500, OH value: 224.4 mgKOH / g, 1,4-butanediol manufactured by Kuraray Co., Ltd. : Reagent, manufactured by Nacalai Tesque Co., Ltd. 2-methyl-1,3-propanediol: MPDiol Glycol, manufactured by Clare Trading Co., Ltd. [Polyamine]
DETDA: EtaCure 100, diethyltoluenediamine, Albemar Japan Co., Ltd. EtaCure 420: 4,4'-methylenebis (N-sec-butylaniline), aromatic secondary diamine, Albemar Co., Ltd. Cure Hard MED: 4,4'- Methylenebis (2-ethyl-6-methylaniline, manufactured by Ihara Chemical Industry Co., Ltd. [catalyst]
Dioctyltin dilaurate: KS-1200A-1, manufactured by Kyodo Yakuhin Co., Ltd. 1-isobutyl-2-methylimidazole: DABCO NC-IM, manufactured by Air Products Japan Co., Ltd. Nikkaoctix Ca 5% TK: Nikkaoctix calcium 5% ( TK), a mixture of 2-ethylhexylate calcium and an isoparaffin solvent, containing 5% as Ca, Tetrahydromethylphthalic anhydride manufactured by Nippon Kagaku Sangyo Co., Ltd .: HN-2200R, tetrahydromethylphthalic anhydride, manufactured by Hitachi Kasei Co., Ltd. 〔solvent〕
MC-2000 Solvent: Normal paraffin, isoparaffin mixture, manufactured by Sankyo Chemical Co., Ltd. [Plasticizer]
DINP: Sunsociizer DINP, Diisononyl phthalate, manufactured by New Japan Chemical Co., Ltd. [Inorganic filler]
Calcium carbonate NS # 100: NS # 100, calcium carbonate, manufactured by Nitto Flour Chemical Co., Ltd. Additives: manufactured by Kusumoto Kasei Co., Ltd. [Commercial waterproofing material]
Alterc Sky: Made by Tajima Roofing Co., Ltd. Alterc Sky UC: Made by Tajima Roofing Co., Ltd. Alterc Sky EX: Made by Tajima Roofing Co., Ltd. Alterc Spray FF: Made by Tajima Roofing Co., Ltd.

Preparation of Main Agent According to the formulation shown in Tables 1 and 3-11, a predetermined polyol, solvent and dioctyltin dilaurate were charged into a four-necked flask, and then a predetermined polyisocyanate compound was charged. Then, the mixture was reacted at 80 to 95 ° C. for 3 to 7 hours with stirring to obtain each main agent.

Preparation of curing agent According to the formulation shown in Tables 1 and 3 to 11, a predetermined liquid is charged in a metal container, mixed at a low speed with a stirrer (dissolver blade) to make it uniform, and then a predetermined amount of calcium carbonate is added and mixed at 1500 rpm for 15 minutes. To obtain each curing agent.

Examples 1 and 2 and Comparative Example 1 (Table 1 fatigue test and zero span tension test)
In Examples 1 and 2 and Comparative Example 1, a main agent and a curing agent were obtained according to the formulation shown in Table 1. These main agent and curing agent were mixed in Example 1 at a mass ratio of 2: 3 and in Example 2 at a mass ratio of 1: 1 to obtain a urethane waterproof material composition.
In Example 1 and Example 2 in which the amino group equivalent per plasticizer was 2.15 meq / g, the tensile product was sufficiently high at 824 and 991 N / mm, respectively, and the fracture energy in the zero span tension test. The elongation at break was also sufficiently high, and passed the A4 category of the JASS8 fatigue test (all three bodies did not break in step III). In addition, as a two-component hand-painted urethane waterproofing material, it was possible to carry out the construction the next day while exhibiting good coating film physical properties and ensuring sufficient pot life. On the other hand, in Comparative Example 1 in which the transamination equivalent per plasticizer was 3.63 meq / g, the tensile strength was 1053 N / mm, which was sufficiently high, but the tensile strength exceeded 10 N / mm ² , but the elongation at break. Since the rate was as low as 450%, some transamination was observed in the A4 category of the zero span tension test and the JASS8 fatigue test. Further, the waterproof material of Comparative Example 1 had a short pot life of 24 minutes, which was unsuitable for construction in summer.

Comparative Examples 2 to 5 (Table 2 Fatigue test and zero span tension test commercially available products)
In Comparative Examples 2 to 5, a commercially available urethane waterproof material was used, and each base agent and curing agent were mixed at a predetermined mixing ratio to obtain a urethane waterproof material composition.
In comparisons 2 and 3 using the general-purpose hand-painted urethane waterproof material, the tensile strength was low, so the tensile product was less than 600 N / mm. The fracture energy in the zero span tension test was as low as 2.5 and 1.7 J, respectively, and the JASS8 fatigue test failed in the A3 category.
In Comparative Example 4 using a high-strength spray material, the tensile strength exceeds 10 N / mm ² , but the elongation at break is as low as 360%. Therefore, some interfaces are used in the A3 category of the zero span tension test and the JASS8 fatigue test. Abnormalities such as peeling were observed.
Comparative Example 5 using the fast-curing hand-coated urethane waterproof material had sufficiently high fracture energy and elongation at break in the zero span tension test, and passed the A4 category of the JASS8 fatigue test. However, the pot life was as short as 27 minutes, which was unsuitable for construction in the summer.

Examples 3 to 7 (Table 3 Amino group equivalents per plasticizer)
In Examples 3 to 7, a main agent and a curing agent were obtained according to the formulation shown in Table 3. The main agent and the curing agent were mixed at a mass ratio of 1: 1 to obtain a urethane waterproof material composition.
Examples 3 to 7 having amino group equivalents of 1.98, 2.18, 2.27, 2.50, and 3.00 meq / g, respectively, have a tensile volume of 600 N / mm or more and zero span. The fracture energy in the tension test and the elongation at break were also sufficiently high, and all of them passed the A4 category of the JASS8 fatigue test (all three bodies did not break in step III). In addition, as a two-component hand-painted urethane waterproofing material, it was possible to carry out the construction the next day while exhibiting good coating film physical properties and ensuring sufficient pot life.

Examples 8 to 11 (Table 4 Formulation of main agent polyol)
In Examples 8 to 11, a main agent and a curing agent were obtained according to the formulation shown in Table 4. The main agent and the curing agent were mixed at a mass ratio of 1: 1 to obtain a urethane waterproof material composition.
Example 8 using Sanniks PP-2000 / New Pole BP-5P / Sanniks GH-5000 = 46/34/20 (equivalent ratio) as the main agent and 41/39/20 (equivalent ratio) were also used. Example 9 using the same 56/34/10 (equivalent ratio), and Example 11 using the same 46/44/10 (equivalent ratio) all had a tensile product of 600 N / mm or more. As a two-component hand-painted urethane waterproofing material, it was possible to construct it the next day while showing good physical properties of the coating film and ensuring sufficient pot life.

Examples 12 to 14 (Table 5 blended with polyol as the main agent)
In Examples 12 to 14, a main agent and a curing agent were obtained according to the formulation shown in Table 5. The main agent and the curing agent were mixed at a mass ratio of 1: 1 to obtain a urethane waterproof material composition.
Example 12 using Sanniks PP-2000 / New Pole BP-5P = 66/34 (equivalent ratio) without using a polyol having 3 or more functional groups as the main agent, also 75/25 (equivalent ratio). Both Example 13 used and Example 14 using 90/10 (equivalent ratio) have a tensile product of 600 N / mm or more, and have good coating film physical properties as a two-component hand-painted urethane waterproof material. It was possible to construct the next day while showing and securing sufficient pot life.

Examples 15 to 17 (Table 6 Diol containing polyol as main agent, molecular weight less than 1500)
In Examples 15 to 17, a main agent and a curing agent were obtained according to the formulation shown in Table 6. These main agent and curing agent were mixed at a mass ratio of 1: 1 to obtain a urethane waterproof material composition.
Example 15 using Clare polyol P-530 as a diol having an average molecular weight of less than 1500 as the main agent, Example 16 using 1,4-butanediol, and Example 17 using 2-methyl-1,3-propanediol. All of them had a tensile weight of 600 N / mm or more, and could be applied the next day while exhibiting good coating film physical properties as a two-component hand-coated urethane waterproof material and ensuring sufficient pot life.

Examples 18 to 20 (Table 7 Curing Accelerator)
In Examples 18 to 20, a main agent and a curing agent were obtained according to the formulation shown in Table 7. The main agent and the curing agent were mixed at a mass ratio of 1: 1 to obtain a urethane waterproof material composition.
Example 18 using 0.10% by mass of 1-isobutyl-2-methylimidazole as a curing agent, Example 19 using 0.01% by mass of dibutyltin dilaurate, and 0% of Nikkaoctix Ca 5% TK as a curing agent. In Example 20 in which 10% by mass was used, the tensile strength was 600 N / mm or more, and while exhibiting good coating physical properties as a two-component hand-coated urethane waterproofing material and ensuring sufficient pot life. Construction was possible the next day.

Examples 21-23 (Table 8 Curing Accelerator Acid Anhydride)
In Examples 21 to 23, a main agent and a curing agent were obtained according to the formulation shown in Table 8. The main agent and the curing agent were mixed at a mass ratio of 1: 1 to obtain a urethane waterproof material composition.
Example 21 in which 0.10% by mass of tetrahydromethylphthalic anhydride was added to the curing agent as a curing accelerator for the acid anhydride, 0.10% by mass of tetrahydromethylphthalic anhydride in the mixture of the main agent and the curing agent. In Examples 22 and 1.00 added, the tensile volume was 600 N / mm or more in both Example 23 in which mass% was added, and the urethane waterproofing material for two-component hand coating showed good coating properties and was sufficient. It was possible to carry out the construction the next day while securing a sufficient pot life. In particular, Example 23 in which 1.00% by mass of tetrahydromethylphthalic anhydride was added to the mixture of the main agent and the curing agent was quick-curing so that the next step could be carried out within the day while ensuring sufficient pot life. became.

Examples 24-27 (Table 9 Main agent NCO / Hardener NH ₂ (equivalent ratio))
In Examples 24 to 27, a main agent and a curing agent were obtained according to the formulation shown in Table 9. The main agent and the curing agent were mixed at a mass ratio of 2: 3 to obtain a urethane waterproof material composition.
Example 24 in which the main agent NCO / curing agent NH ₂ (equivalent ratio) is 0.95, Example 25 in 1.05, Example 26 in 1.10, and Example 22 in 1.15 are all tensile strength. Was 600 N / mm or more, and it was possible to carry out the next day construction while exhibiting good coating film physical properties as a two-component hand-coated urethane waterproofing material and ensuring sufficient pot life.

Examples 28 to 31 (Table 10 Main agent NCO / curing agent NH ₂ (equivalent ratio), curing accelerator used)
In Examples 28 to 31, a main agent and a curing agent were obtained according to the formulation shown in Table 10. The main agent and the curing agent were mixed at a mass ratio of 2: 3 to obtain a urethane waterproof material composition.
Example 28 in which the main agent NCO / curing agent NH ₂ (equivalent ratio) was 1.15 and 1-isocyanate-2-methylimidazole was used in an amount of 0.50% by mass as the curing agent, the main agent NCO / curing agent NH ₂ (equivalent ratio) In Example 29, when 0.50% by mass of 1-isocyanate-2-methylimidazole was used as the curing agent at 1.20, the main agent NCO / curing agent NH ₂ (equivalent ratio) was 1.20 and dibutyltin dilaurate was used as the curing agent. Example 30 in which 0.01% by mass was used, Example 31 in which the main agent NCO / curing agent NH ₂ (equivalent ratio) was 1.27 and 1-isocyanate-2-methylimidazole was used as the curing agent in an amount of 0.50% by mass. All of them had a tensile strength of 600 N / mm or more, and could be applied the next day while exhibiting good coating properties as a two-component hand-coated urethane waterproofing material and ensuring sufficient pot life.

Examples 32 to 34 (Table 11 Combined use of active hydrogen compounds other than DETDA)
1.96% by mass of EtaCure 420 is used as a curing agent, DETDA (equivalent%) in the aromatic polyamine of the curing agent is 85, aromatic polyamine / other active hydrogen (equivalent ratio) is 100/0, and the main agent NCO / Example 32 having a curing agent NH ₂ (equivalent ratio) of 1.05, 1.14% by mass of Cure Hard MED was used as the curing agent, and DETDA (equivalent%) in the aromatic polyamine of the curing agent was 85, aromatic. Example 33 in which polyamine / other active hydrogen (equivalent ratio) is 100/0, main agent NCO / curing agent NH ₂ (equivalent ratio) is 1.05, and 2.04% by mass of Clare polyol P-530 is used as the curing agent. However, DETDA (equivalent%) in the aromatic polyamine of the curing agent is 100, aromatic polyamine / other active hydrogen (equivalent ratio) is 85/15, and the main agent NCO / curing agent NH ₂ (equivalent ratio) is 1.24. In Example 34, the tensile volume is 600 N / mm or more, and the next day construction is possible while exhibiting good coating material properties as a two-component hand-coated urethane waterproofing material and ensuring sufficient pot life. Met.

The measurement method for each evaluation item is as follows.

[NCO (mass%)]
About 1 g of the main ingredient is precisely weighed in a 200 mL Erlenmeyer flask, and 10 mL of 0.5 N-n-butylamine (toluene solution), 10 mL of toluene and an appropriate amount of bromphenol blue are added thereto, and then about 100 mL of methanol is added to dissolve the mixture. The mixture is titrated with a 0.25N hydrochloric acid solution. NCO (mass%) is calculated by the following formula.
NCO (mass%) = (blank titration value-0.5N hydrochloric acid solution titration value) x 4.202 x 0.25N hydrochloric acid solution factor x 0.25 / sample weight

[Available time (minutes)]
In an air circulation type environmental test room at 23 ° C. and 50% humidity, the time from the start of stirring and mixing the main agent and the curing agent at a predetermined ratio until the viscosity at 2 rpm reaches 60,000 mPa · s with a BH type viscometer. It was measured.

[Construction time (hours)]
In an air circulation type environmental test room at 23 ° C and 50% humidity, 2 kg / m ^{2 of} a waterproof material in which the main agent and the curing agent were agitated and mixed at a predetermined ratio was applied, and although it was not completely cured, it was not completely cured, but with shoes. The time when walking became possible and the work of the next process could be started was measured.

[Tensile strength (N / mm ² )]
Measurements were made based on JIS A 6021.

[Elongation rate at break (%)]
Measurements were made based on JIS A 6021.

[Tear strength (N / mm)]
Measurements were made based on JIS A 6021.

[Tension product (N / mm)]
Calculations were made based on JIS A 6021 using the above tensile strength and elongation at break.

[Hardness (Type A durometer)]
Measurements were made based on JIS K 6253.

[Preparation of zero span tension test piece]
A slit with a width of 5 mm is inserted in the center of the back surface of a 400 mm × 150 mm × 8 mm asbestos slate flexible plate in the longitudinal direction to a depth of 6 mm. Next, a primer is applied to the surface of the asbestos slate flexible plate. After the primer is dried, the urethane waterproof material composition is applied at a size of 300 mm × 100 mm × 2 mm (coating film thickness), and the test piece is cured in an air circulation type environmental test room at 23 ° C. and 50% humidity for 1 week. And said.
A schematic diagram of the test piece is shown in FIG. (A) is a plan view and (b) is a front view. 1 is a test body, 2 is an asbestos slate flexible plate, 3 is a urethane coating film waterproof layer, 4 is a slit, 5 is a base crack position, and 6 is a hole for fixing.

[Zero span tension test method]
Fold the slit part of the test piece and make a crack in the asbestos slate flexible plate. Set in a tensile tester and pull both ends of the asbestos slate flexible plate in the longitudinal direction at a low speed of 0.5 mm for 1 minute to break the distance = elongation at break (mm) and total energy to break = fracture energy (J) was measured.

[JASS8 fatigue test]
Based on "JASS8 T501 Membrane Waterproof Layer Performance Evaluation Test Method 3.3 Fatigue Test", evaluation was performed using an A-type test piece (coating thickness 2 mm). The test process diagram is shown in FIG.

The composition of the present invention can be suitably used as a high-tensile two-component environment-friendly hand-coated urethane waterproofing material for waterproofing the rooftop of a building or the veranda of an apartment house such as an apartment.

1 Specimen 2 Asbestos slate flexible plate 3 Urethane coating waterproof layer 4 Slit 5 Base crack position 6 Fixing hole

Claims (10)

A two-component hand-painted urethane waterproofing composition composed of a main agent containing an isocyanate group-terminated prepolymer composed of a polyisocyanate and a polyol, and a curing agent containing an aromatic polyamine as a reaction component, a plasticizer, and an inorganic filler. And
A 70 equivalent percent isophorone diisocyanate main agent of polyisocyanate, diol polyol base resin comprises a polyoxyalkylene polyol, polyol base resin has a molecular weight of 1500 or more diols below 20 to 97 equivalent percent and molecular weight 1500 And a polyol having 3 or more functional groups are contained in an amount of 3 to 80 equivalents, and the NCO content of the isocyanate group-terminated prepolymer is more than 2.3% by mass and 5.5% by mass or less.
The curing agent contains more than 80 equivalents of aromatic polyamines in the total reaction components, the aromatic polyamines containing diethyltoluenediamine, and 20-80% by mass of an inorganic filler.
The plasticizer is blended in the curing agent or in both the main agent and the curing agent so that the amount of the plasticizer is 16 to 80 parts by mass with respect to 100 parts by mass of the prepolymer in the main agent.
The ratio of amino group amount (milli equivalent) / plasticizer amount (g ) of aromatic polyamine in the mixture of the main agent and the curing agent is 1.6 to 3.4.
A two-component hand-coated urethane waterproofing material composition in which the equivalent ratio of the amino groups of aromatic polyamines, which are the reaction components in the isocyanate group / curing agent of the main agent, is 0.9 to 1.4. The two-component hand coating according to claim 1, wherein the ratio of the amino group amount (milli equivalent) / plasticizer amount (g ) of the aromatic polyamine in the mixture of the main agent and the curing agent is 1.6 to 3.0. Urethane waterproof material composition. The two-component hand-coated urethane waterproof according to claim 1 or 2, wherein the equivalent ratio of the amino group of the aromatic polyamine which is the reaction component in the isocyanate group of the main agent / the curing agent is 0.92 to 1.24. Material composition. At least one selected from the group consisting of an organic stannic compound, a metal carboxylic acid salt, a carboxylic acid, an acid anhydride and a tertiary amine as a reaction accelerator in a main agent, a curing agent or a mixture of a main agent and a curing agent. The two-component hand-coated urethane waterproof material composition according to any one of claims 1 to 3, wherein the seeds are blended. The two-component hand-painted urethane waterproofing material according to any one of claims 1 to 4, wherein an organic stannic compound or an imidazole compound is blended in a main agent, a curing agent, or a mixture of the main agent and a curing agent. Composition. The two-component hand-coated urethane waterproof material composition according to any one of claims 1 to 5 , wherein more than 50 equivalent% of the main agent polyol is a polyoxyalkylene polyol. The two-component hand-coated urethane waterproof material composition according to any one of claims 1 to 6 , wherein more than 70 equivalent% of the aromatic polyamine is diethyl toluenediamine. The two-component hand-coated urethane waterproof material composition according to any one of claims 1 to 7 , wherein the tensile product is 600 N / mm or more. The two-component hand-coated urethane waterproof material composition according to any one of claims 1 to 8 , after applying a primer layer or a primer layer and a urethane waterproof material layer to the adherend. Urethane waterproofing method including the process of applying a primer. A two-component hand-painted urethane waterproof according to any one of claims 1 to 8 after applying a ventilation buffer sheet, a polymer sheet, a root-proof sheet or a polymer paint film material to the adherend. Urethane waterproofing method including the process of applying the material composition.

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