JP6706887B2 - High-strength two-component environment-friendly hand-painted urethane waterproofing material composition and urethane waterproofing method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a high-strength two-component environment-friendly hand-painted urethane waterproof material composition and a urethane waterproofing method using the composition.

Urethane waterproofing materials are suitable for construction of irregular shapes and narrow areas, so waterproofing of balconies and eaves of condominiums and other eaves, rooftops with many accessories, etc. It has been widely used for rooftop waterproofing. A general urethane waterproofing material is one in which two liquids are mixed with a stirrer and then hand-painted with a trowel, spatula, roller, brush, etc., and usable time of at least 30 minutes after mixing with a stirrer. (Hereinafter referred to as the pot life) is required.
The above-mentioned two-component urethane waterproof material for hand-painting has a large difference in outside air temperature between winter construction and summer construction. Therefore, a summer mix suitable for construction around 30°C in summer and 10°C in winter It is common to prepare winter mixes suitable for front and rear construction. For example, in summer mixes, the pot life at 23°C is 40 minutes or more, and in winter mixes, 23°C is possible. The usage time is about 20 minutes or more. The pot life is generally the time after the two liquids are mixed at 23° C. until the viscosity reaches 60,000 to 100,000 mPa·s.
Further, it is desired that the urethane waterproofing material be applied in the evening and hardened so that the user can walk lightly in the morning of the next day, and it is best that the curing time can be adjusted within 17 hours throughout the year.

The performance of urethane waterproof materials is specified in detail in JIS A 6021, coating film waterproof materials for construction. For hand-coating materials that have been widely used in the past, the elongation at break (hereinafter referred to as elongation The tensile strength is defined as 450% or more, the tensile strength is 2.3 N/mm ² or more, and the tensile product is 280 N/mm or more. On the other hand, ultra-fast curing spray coating, in which two highly reactive components are collision-mixed and applied by a special spray device, is used for special purposes such as waterproofing for parking lots, waterproofing for rooftop greening, waterproofing for metal roofs, and waterproofing for civil engineering. It has come to be used. This material has high reactivity and can walk in a few minutes after construction, resulting in high strength. However, it is somewhat difficult to secure the elongation rate, and the elongation rate is 200% or more and the tensile strength is 10 N/ With a standard of mm ² or more and a tensile product of 700 N/mm, it has recently come to be classified as a urethane rubber high strength type in JIS A6021. Tensile product=(tensile strength×elongation rate)/5, which is difficult to achieve by simply increasing tensile strength in order to increase tensile product. It becomes important. In spray construction, scattering of mist generated during spray construction is a big problem, and in addition to carefully curing the vicinity of the construction with film etc., you must pay attention to nearby houses and cars as well. Not suitable for construction in dense residential areas. Further, since the spray device is expensive and requires a dedicated engineer, there is a problem that the construction shops that can be installed are limited.

The high-strength urethane waterproof material for hand-coating that is currently in widespread use is mainly composed of an isocyanate group-terminated prepolymer consisting of tolylene diisocyanate (hereinafter referred to as TDI) and polyoxypropylene polyol. In addition, as a reaction component, an aromatic polyamine having a relatively mild reaction, 3,3′-dichloro-4,4′-diaminodiphenylmethane (hereinafter referred to as MOCA) as a main component, is a low-reactivity secondary polyol. A polyoxypropylene polyol is used in combination. In that case, it is common to use lead carboxylate as a catalyst in the curing agent, which is said to have a foaming-preventing effect by selectively promoting the reaction with the polyol rather than water. The material is called MOCA cross-linked waterproof material. Note that calcium carbonate is generally mixed as an inorganic filler in the curing agent, but calcium carbonate contains about 0.1 to 0.3% by mass of water, and other than lead carboxylate. This catalyst also promotes the reaction with this water, and it is said that the carbon dioxide gas produced as a by-product is likely to cause a foaming phenomenon in the coating film especially in summer.

Since the MOCA cross-linking type waterproof material has a mild reactivity, it has excellent workability especially in the summer when pot life is required, and because it has relatively good mechanical strength, it is still a general-purpose waterproof material. It is used. In addition, many general-purpose urethane waterproof materials have an NCO content of about 4.0% by mass as the base material, but the NCO content is increased to around 6.0% by mass, which is a reaction component in the curing agent. Urethane flooring for hand-painting, which has been strengthened by increasing the concentration of MOCA, has also been developed for a long time, but because it has many indoor applications and has a large NCO content in outdoor summer construction. A foaming phenomenon due to a reaction with water tends to occur, and when a large amount of lead carboxylate is added to prevent foaming, it is difficult to secure a usable life.

The MOCA cross-linking waterproof material has a serious environmental problem. The MOCA used as a curing agent is designated as a Class 2 substance for specified chemical substances in the Industrial Safety and Health Act, and since it exceeds 1% of the upper limit value for the curing agent, damage to specified chemical substances, etc. Preventive rules (hereinafter referred to as special rules) are applicable products. In addition, MOCA is classified into Group 1 (which shows carcinogenicity to humans) by carcinogenicity evaluation by IARC (International Cancer Research Institute).
In addition, the TDI used in the main ingredient is also specified as a specific chemical substance, and free TDI is present in the main ingredient of general-purpose products in excess of 1% of the upper limit value, so the main ingredient also complies with the special rules. Therefore, various restrictions are imposed during manufacturing and construction. Furthermore, the lead carboxylate compound used as a catalyst is a material whose use is strictly restricted worldwide, and is designated as a specified Class 1 designated chemical substance under the Chemical Substance Emissions Control Law (commonly known as the tube shift method). However, from the environmental point of view, it is a material that should not be used.

On the other hand, the high-strength urethane waterproof material for spray construction has an NCO content of about 10 mass% consisting of a partial prepolymer of diphenylmethane diisocyanate (hereinafter referred to as MDI), which is more reactive than TDI, and a polyol. As a main component of the reaction component in the curing agent, highly reactive and highly cohesive diethyltoluenediamine (hereinafter referred to as DETDA) is used, and polyoxyethylene propylene polyol (OH It is general to add about 70 equivalent% of the group to primary. Also in this case, it is general to use lead carboxylate as the catalyst mainly for promoting the reaction with the polyol. It is gelled within a few seconds after the sprayed material is applied. It is easy to increase the strength, but it is difficult to increase the elongation a little.
Further, when the amount of the plasticizer is increased, the gelation time becomes longer and the fluidity is generated, which may make it difficult to secure the film thickness, and there is also a feature that the amount of the plasticizer is smaller than that for hand coating. MDI and DETDA do not correspond to specified chemical substances.

In addition, as a high-stretch urethane waterproof material for hand coating, a type called a DETDA cross-linking waterproof material, which uses DETDA as a reaction component with respect to a TDI prepolymer, has been commercialized. The DETDA cross-linking waterproof material has been designed so that the TDI in the main component is also 1% or less, and since it is not necessary to use lead carboxylate as a catalyst, it is an environment-friendly waterproof material that does not meet the special rules. (Patent Document 2).
DETDA cross-linking type waterproof material has the characteristic that it has good curability even at low temperatures, but since it is difficult to secure a pot life in summer, a large amount of plasticizer is added, and a special TDI method is used. (Patent Document 1), a method of using an aromatic polyester polyol in combination (Patent Document 2), and the like have been proposed to secure a usable time. However, in order to increase the strength of the DETDA crosslinkable waterproof material in the urethane waterproof material for hand-coating, it is necessary to add more DETDA which is highly reactive and highly cohesive, and the pot life must be secured. Becomes very difficult. Since DETDA is much more reactive than water, the coating film containing DETDA as a main reaction component has an advantage that the effect of suppressing the foaming phenomenon is higher than that of the MOCA cross-linking waterproof material even without lead carboxylate.

Next, regarding the method of using the urethane waterproof material, the function of ensuring the adhesiveness with the adherend and the water content of the adherend are not applied directly to the adherend of an inorganic substance such as concrete or a metal. In principle, it is applied after applying a primer having a function of insulating The urethane waterproofing material itself has poor adhesion to concrete and metal, and if it is applied directly to an adherend that contains a lot of water, it will become foamy, so it has not been applied directly and has a large area. In the construction of, in order to avoid the influence of moisture in the concrete layer as much as possible, it is general to use a method with a deaeration function using a ventilation cushioning sheet.
Further, since the urethane waterproof material itself has insufficient weather resistance, it is a principle to apply a top coat having good weather resistance after applying the urethane waterproof material.

As a conventional technique, as a method for forming a coating on a mineral building material, an isocyanate group-terminated prepolymer composed of isophorone diisocyanate (hereinafter referred to as IPDI) and a polyol is cured by DETDA to form an adherend containing water. Although there is a technique of directly applying and protecting the adherend (Patent Document 3), the construction method and the required performance are greatly different, and the urethane waterproof material of the present application not only satisfies the JIS standard whose details are specified, but also throughout the year. It also relates to a compounding that takes into consideration the optimum workability and long-term durability.
Further, there is also a urethane waterproof material technology (patent document 4) in which an isocyanate group-terminated prepolymer composed of IPDI and polyester polyol is used as a main component, and DETDA in a curing agent is used as a reaction component, and a top coat is not required to be applied. It has been reported that urethane coatings using polyester polyols are generally excellent in weather resistance and heat resistance, but ester bonds are susceptible to hydrolysis and are said to be inferior in water resistance and alkali resistance. (Non-patent document 1).
Furthermore, there is also a technique of using DETDA as a reaction component of a curing agent and using TDI prepolymer and IPDI prepolymer together as a main component to secure a pot life (Patent Document 5), but when the main component is only an IPDI prepolymer. Indicates that there is a problem in curability at low temperatures and that the physical properties as a urethane waterproof material are insufficient.
Recently, a non-bleed, high strength, high elongation type hand-painted urethane waterproof material composition containing DETDA, water and polyol as essential reaction components and a small amount of a special plasticizer to IPDI prepolymer using a special polyol. Although the technology (Patent Document 6) is disclosed, the physical properties are high strength by heating at 60°C instead of the curing condition of 23°C specified in the JIS standard (waterproofing material for building, JIS A 6021). A method of making it waterproof has been shown, and it is a waterproofing technology mainly intended for coating on asphalt-based substrates.

Japanese Patent No. 3114557 JP, 2013-139559, A JP-A-58-134160 JP, 10-17819, A JP-A-9-183942 JP, 2014-227522, A

Nishijima Hiroshi, "Complete Polyurethane Design/Modification and Functionalization Technology", Technical Information Association, March 31, 2007, p. 44

There is no major problem in clearing the standard of urethane rubber high strength type of JIS A 6021 architectural coating waterproof material with a super fast curing spray material. However, spray construction has a big problem of mist scattering, and the places where it can be constructed are limited. In addition, since the spray device is expensive and requires a specialized technician, the number of construction shops is limited, and there is a limit to its widespread use. In terms of environment, since the material is heated to around 60° C. and sprayed at a high pressure, there is a risk that an operator may inhale MDI vapor and that lead carboxylate is used. is there.

On the other hand, there is a big problem in applying the conventional urethane waterproof material for hand-coating to the high strength type.
In the case of the conventional MOCA cross-linking type waterproof material, when the NCO content of the main component is increased in order to increase the strength, the foaming property during the summer construction becomes severe as described above, and the carbonization is performed to reduce the foaming property. If lead acid is added in a large amount, there is a problem that the pot life is shortened. From the environmental aspect, it is also desirable to avoid further providing the market with waterproof materials that meet the special rules, and also to avoid environmental pollution due to lead carboxylate.
Further, in the conventional DETDA cross-linking type waterproof material, it is necessary to increase the NCO content and to use a large amount of highly reactive DETDA in order to increase the strength, but this method further shortens the pot life. There is also the problem that construction in summer will be difficult.

The waterproofing material that uses IPDI and polyester polyol as the main component and DETDA as the curing agent has a very high viscosity because of the high viscosity of the polyester polyol. Especially, the removal and mixing of the main component from the can during winter construction Becomes difficult. In order to solve this problem, it is necessary to add a large amount of solvent, but the deterioration of the working environment due to the solvent and the reduction in the thickness of the waterproof layer due to solvent volatilization after construction, the occurrence of peeling and cracks at the edge due to shrinkage Problems are more likely to occur. In particular, a material having a large amount of solvent is not suitable for the construction of the urethane waterproof material which requires a thickness of about 1.5 to 2.5 mm for one construction.

Further, the above-mentioned technique uses a liquid aliphatic polyester polyol having a low crystallinity, but in particular, the aliphatic polyester polyol has a problem in hydrolysis resistance, alkali resistance, and bacterium resistance, and therefore concrete construction that is alkaline It is unsuitable for use in the area around objects, rooftop greening, and civil engineering, and it is hard to say that it is suitable for high-strength urethane waterproof materials.
The use of aromatic polyester polyols may alleviate the above-mentioned weaknesses to some extent, but since the viscosity is higher than that of aliphatic polyester polyols, the construction problem becomes more serious.

Note that the urethane rubber-based high-strength type standard has an elongation of 200% or more, but the conventional knowledge shows that the elongation of the waterproof material should be increased for adherends such as concrete that crack. It is recognized that it is important that even if it is a high strength type when it is applied to an inorganic base such as a concrete base, if the elongation rate can be 300% or more, it should be as high as 450% or more like the high elongation type. It is desirable to secure crack followability, which is a characteristic of urethane waterproof materials.

The present invention comprises a main agent containing an isocyanate group-terminated prepolymer composed of polyisocyanate and a polyol, and a curing agent containing an aromatic polyamine, a plasticizer and an inorganic filler, and JIS A 6021 (coating waterproofing material for construction). ) This is a 2-pack environment-friendly hand-painted urethane waterproof material that is applicable to the urethane rubber type high strength type and has good workability and versatility. For the conventional urethane waterproof material, the main ingredient is a polyisocyanate component. As a polyol component, a general-purpose polyoxyalkylene polyol having low viscosity and excellent hydrolysis resistance is used, and one of the curing agents has a highly reactive fragrance. This has been accomplished by using DETDA, which is a group polyamine, and a versatile plasticizer and filler, and mixing the isocyanate group of the main agent and the aromatic amino group of the curing agent in a specific equivalent ratio.

The present invention includes the following aspects.
[1] A two-pack type eco-friendly hand coating consisting of a main agent containing an isocyanate group-terminated prepolymer composed of polyisocyanate and a polyol, and a curing agent containing an aromatic polyamine as a reaction component, a plasticizer and an inorganic filler. A urethane waterproof material composition,
a) The main component polyisocyanate contains isophorone diisocyanate, the main component polyol contains a polyoxyalkylene polyol, and the main component polyol contains 10 to 97 equivalent% of a diol having a molecular weight of 1500 or more and a diol having a molecular weight of less than 1500 and the number of functional groups. 3 to 90 equivalent% including 3 or more polyols in total, the NCO content of the isocyanate group-terminated prepolymer is more than 3.0% by mass and 6.0% by mass or less,
b) The curing agent has an aromatic polyamine in an amount of more than 90 equivalent% in all reaction components, the aromatic polyamine contains diethyltoluenediamine, and the inorganic filler contains 20 to 80% by mass.
c) The plasticizer is blended with the curing agent, or divided into both the main agent and the curing agent, so as to be 16 to 60 parts by weight with respect to 100 parts by weight of the prepolymer in the main agent,
Two-component environment-friendly, with an equivalent ratio (isocyanate group/aromatic amino group) between the isocyanate group of the main agent and the amino group of the aromatic polyamine that is the reaction component in the curing agent is 0.92 to 1.24. Urethane waterproofing material composition for hand coating.
[2] selected from the group consisting of an organic stannic compound, a carboxylic acid metal salt, a carboxylic acid, an acid anhydride and a tertiary amine as a reaction accelerator in the main agent, the curing agent or the mixture of the main agent and the curing agent. The two-component environment-friendly hand-coating urethane waterproof material composition according to [1], which contains at least one of the following.
[3] The two-component environment-friendly hand-coating urethane according to [1] or [2], in which an organic stannic tin compound or an imidazole compound is mixed in a main agent, a curing agent, or a mixture of the main agent and a curing agent. Waterproof material composition.
[4] The two-component environment-friendly hand-coating urethane waterproof material composition according to any one of [1] to [3], in which more than 70 equivalent% of polyisocyanate is isophorone diisocyanate.
[5] The two-component environment-friendly hand-coating urethane waterproof material composition according to any one of [1] to [4], in which more than 50 equivalent% of the base polyol is a polyoxyalkylene polyol.
[6] The two-component environment-friendly hand-coating urethane waterproof material composition according to any one of [1] to [5], wherein more than 70 equivalent% of the aromatic polyamine is diethyltoluenediamine.
[7] The two-component environment-friendly hand according to any one of [1] to [6] after applying the primer layer or the primer layer and the urethane waterproof material layer to the adherend. A urethane waterproofing method including a step of applying a urethane waterproofing material composition for coating.
[8] The two-pack type according to any one of [1] to [6] after the air-permeable cushioning sheet, the polymer sheet, the root preventive sheet or the polymer coating film material is applied to the adherend. Urethane waterproofing method of applying environmentally friendly urethane waterproofing material composition for hand coating.

The two-component environment-friendly urethane waterproof material for hand-coating of the present invention can correspond to the urethane rubber high strength type of JIS A 6021 (coating waterproof material for construction), has a low viscosity, and has a workability throughout the year. Excellent in durability such as hydrolysis resistance, weather resistance, and heat resistance required for high-strength type, and also has crack followability required for concrete-based groundwork, environmentally friendly Has been done.

(Isocyanate group/aromatic amino group equivalent ratio)
Since the conventional DETDA cross-linking waterproof material is highly reactive, it has a drawback that it is difficult to secure a pot life. In particular, it is difficult to secure a pot life in summer, and in order to make the pot life as long as possible, the equivalent ratio of the isocyanate group of the main agent to the aromatic amino group of DETDA (isocyanate group/aromatic amino group) It is generally practiced to add a small amount of DETDA so as to be about 1.2 to 1.3.
In such a case, the excess NCO groups remaining without reacting with DETDA are water adhering to the inorganic filler compounded in the curing agent, water taken up from the air when mixing the two liquids (moisture), and further After being applied, it gently reacts with moisture (moisture) absorbed from the surface of the coating film and self-crosslinks, so that the cured product has a higher molecular weight and higher strength.
Further, even if the (isocyanate group/aromatic amino group) is increased to 1.2 to 1.3, DETDA is highly reactive, so that the cured coating film can walk sufficiently in the next morning even at a low temperature. It can be a fast-curing waterproof material that exhibits moderate strength.

In addition, JIS A 6021 (coating waterproof material for buildings) stipulates that physical properties should be measured after 7 days in a standard condition where the waterproofing property of the waterproof membrane is 23±2° C. and the humidity is 50±10%. However, in the conventional MOCA cross-linking waterproofing material and DETDA cross-linking waterproofing material containing TDI prepolymer as the main component, self-crosslinking due to the reaction between the excess isocyanate group and water is mostly completed in the curing period of 7 days. The maximum strength has been reached. Therefore, it is common to measure physical properties immediately after curing for 7 days in a standard state.

On the other hand, it was found that the curing process of the DETDA cross-linking waterproof material containing the IPDI prepolymer as the main component of the present application is significantly different from the conventional one. Under the condition that the NCO content of the main agent was constant, the DETDA amount was adjusted so that (isocyanate group/aromatic amino group) was in the range of 0.9 to 1.3. It was found that the physical properties had a peak in the vicinity of (isocyanate group/aromatic amino group) 1.0 to 1.05, and when it was 1.10 or more, the physical properties tended to deteriorate unlike conventional products.
This is because the terminal isocyanate group of the IPDI prepolymer is a low-reactivity secondary isocyanate group, so the reaction with water is very slow, and the excess isocyanate group is not observed after 7 days in the standard state. This is probably because the self-crosslinking did not proceed so much. However, since the reaction between the IPDI prepolymer and DETDA proceeds relatively quickly even at room temperature, it can develop strength and become a walkable waterproof material on the next day.

In the present application, even if the (isocyanate group/aromatic amino group) is around 1.0, the pot life is longer than that of the conventional DETDA cross-linking waterproof material, so that it is not a practical problem. Further, in order to increase the strength of the conventional DETDA cross-linking waterproof material, it is effective to increase the NCO content of the main agent and increase the DETDA amount in the curing agent, but this method has a usable life of In the present application, even if the NCO content is further increased, the pot life can be secured and higher strength can be achieved, while it becomes shorter and is not practical.

(Curing condition)
As a result of further studying the enhancement of strength, it was found that the waterproof material of the present invention has significantly improved physical properties after 14 days in the standard state, compared with those after 7 days. This tendency becomes remarkable as the (isocyanate group/aromatic amino group) becomes slightly higher from 1.05 to 1.20, and thus self-crosslinking due to the reaction between the terminal isocyanate group of the IPDI prepolymer and water is also caused. It is presumed that it is difficult to proceed.
However, it was found that if the (isocyanate group/aromatic amino group) becomes too high, the effect of reducing the amount of DETDA used becomes large, and it is difficult to easily increase the strength even after 14 days in the standard state. ..
It is noted that the physical properties are significantly increased between 7 and 14 days after curing in the standard condition, but the physical properties after 14 days and 28 days are not so different. Therefore, in the present application, it was decided that the high strength after 14 days in the standard state should be within the scope of the invention.

As described above, the waterproof material using the IPDI prepolymer of the present application requires a little time to reach the maximum strength as compared with the conventional product, but since the reaction with DETDA progresses relatively smoothly, walking by the next morning It is cured to such an extent that it becomes a practical high-strength two-component environment-friendly hand-painted waterproof material capable of achieving high strength at room temperature.

As described above, the (isocyanate group/aromatic amino group) plays a dominant role for increasing the strength, and it is an effective means to bring it closer to 1.0. However, when it is less than 1.0, the amount of low molecular weight amino group-terminated products in the cured product increases, and the physical properties tend to gradually decrease. Since low molecular weight compounds with terminal amino groups cannot polymerize further, if (isocyanate group/aromatic amino group) is made too low, it will stop with low strength and heat resistance etc. It will be in a dangerous state that the durability of will also deteriorate.
Further, if the (isocyanate group/aromatic amino group) becomes too low, the NCO group in the cured product becomes difficult to remain, so that the adhesiveness with the waterproof material or the top coat applied thereon is reduced. Problems also occur. From the above, in the present invention, (isocyanate group/aromatic amino group) needs to be 0.92 to 1.24, preferably 0.95 or more and less than 1.20, More preferably, it is 97 to 1.17.

(Reaction accelerator)
As a result of further deep investigation, it was found that in the waterproof material of the present application, by using the moisture curing accelerator, it is possible to achieve high strength in a shorter period of time. This effect tends to be particularly remarkable in the range of (isocyanate group/aromatic amino group) of 1.05 or more, and more preferably 1.10 or more, so that a higher (isocyanate group/aromatic amino group) is obtained. Even if it is set, high strength can be achieved quickly, it will be a safer side against lowering of the mixing ratio during construction, and it will be effective in terms of securing the working life.

In the present application, organic stannic compounds, tertiary amines, carboxylic acid metal salts, etc., which are said to have a moisture curing promoting effect in the urethanization reaction, can be used as the reaction accelerator.
Examples of the organic stannic compound include dibutyltin oxide, dioctyltin oxide, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin di2-ethylhexanoate, dioctyltin diacetate, dioctyltin dilaurate, dibutyltin dimercaptide, dibutyl. Examples thereof include tin bisacetylacetonate, dibutyltin oxylaurate, dioctyltin dyneodecanate, dibutyltin bisbutylmalate, dioctyltin 2-ethylhexylmalate, and among them, dibutyltin dilaurate and dioctyltin dilaurate are preferable. It is preferable to use 0.001 to 0.1 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. The imidazole compound, which is a special tertiary amine, is preferable from the viewpoint of the effect of suppressing foaming and promoting high-strength expression. Examples of the imidazole compound include 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-benzyl- Compounds having a substituent at the 1-position and 2-position such as 2-methylimidazole and 1-benzyl-2-phenylimidazole, and compounds having a substituent at the 1-position such as 1-methylimidazole and 1-allylimidazole are Can be used. Among them, the imidazole compound having a substituent at the 1-position and the 2-position is more preferable because it has a high strength development promoting effect. It is preferable to use the tertiary amine in the curing agent in an amount of 0.01 to 2.0% by mass.

Further, a carboxylic acid metal salt which is generally a urethanization catalyst can also be used. Although the carboxylic acid metal salt has a weak effect of promoting moisture curing, it strongly accelerates the reaction with the aromatic polyamine and shortens the pot life and the curing time. Therefore, it is preferably used 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, zirconium zirconium 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 strength-enhancing effect. The carboxylic acid metal salt is preferably used in the curing agent in an amount of 0.1 to 4.0% by mass. 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 recognized so much, and it is not preferable to use it in terms of environment.

As described above, compounds that are thought to promote moisture curing can be used, but among them, organic stannic compounds and imidazole compounds should promote high strength without shortening the pot life. It is also possible to use it as a catalyst for the summer, because it has excellent foaming-inhibiting property.
Further, the imidazole compound is more preferable because it has a strong tendency to promote thermal deterioration when a large amount of a metal-based catalyst is added, whereas it has a characteristic that it hardly promotes thermal deterioration even if 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 when the two liquids are mixed at the construction site. On the other hand, although it is possible to mix it in the main agent side, it is not 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, and thus is effective in shortening the pot life and the curing time, and also promotes the thermal deterioration such as carboxylic acid metal salt. Since it does not exist, it can be preferably used as an accelerator for winter. However, since there is almost no effect of promoting moisture curing, the effect of promoting high-strength development cannot be expected so much in a composition having a high (isocyanate group/aromatic amino group).
Examples of the carboxylic acid include propionic acid, 2-methylpentanoic acid, octylic acid, isononanoic acid, naphthenic acid, etc. Among them, octylic 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 them, methyl-tetrahydrophthalic anhydride is mentioned. preferable.
The carboxylic acid and the acid anhydride are preferably used in an amount of 0.05 to 2.0% by mass in the curing agent, and a part or the whole amount thereof may be added to the main agent side.

Furthermore, when a detailed study was conducted on the acid anhydride catalyst, the acid anhydride itself does not have a reaction promoting effect, but when compounded on the curing agent side, it is hydrolyzed by the water contained in the curing agent to give a corresponding dicarboxylic acid. Therefore, it has been found that a considerable part acts as a carboxylic acid catalyst in the step of mixing with the main agent, and shortens the pot life and the curing time.
On the other hand, when it is blended in the main agent side, the acid anhydride is stable because it is an anhydrous system, and after the start of mixing with the curing agent, hydrolysis starts with the water in the curing agent, but the reaction is the isocyanate of the prepolymer. Being competitive with the nate group, it does not significantly affect the pot life and can ultimately reduce the cure time. Therefore, it has been found that by adding an acid anhydride to the main agent side, the waterproof material has the most preferable workability in that the pot life is sufficiently longer than that of the conventional waterproof material and that it is cured quickly.

Also, the hydrolysis reaction rate of the acid anhydride can be adjusted by adding a small amount of water to the curing agent in advance. Furthermore, it can be used in combination with a moisture curing accelerator. There is also a method of adding an acid anhydride at the time of mixing two liquids at a construction site, but adding a very small amount of an acid anhydride in small portions at the construction site may cause a decrease in workability and trouble, In addition, when the acid anhydride is handled at the construction site, it may be hydrolyzed by moisture or moisture, which is difficult to manage, which is not preferable.
In addition, any one or more accelerators of organic stannic compounds, carboxylic acid metal salts, carboxylic acids, acid anhydrides and tertiary amines can be used in combination.

As described above, according to the present application, the curing condition of the conventional standard condition of 7 days was extended to 14 days, and the moisture curing accelerator was used in some cases, so that the (isocyanate group/aromatic amino group) equivalent ratio was 0.92. In the range of up to 1.24, it can be a two-component environment-friendly hand-painted urethane waterproof material that has high strength and excellent workability throughout the year. From the viewpoint of more excellent strength development and higher strength, (isocyanate group/aromatic amino group) is preferably 0.95 or more and less than 1.20, and 0.97 to 1.17. More preferably. In order to increase the strength, the equivalent ratio of the aromatic amino group containing DETDA as a main component is dominant, and even if a moisture curing accelerator is used, (isocyanate group/aromatic amino group) is 1.24. When it exceeds, it becomes difficult to achieve high strength.

(Active hydrogen in curing agent)
Next, intentional blending of water and polyol other than the aromatic polyamine as a reaction component in the curing agent was examined. First of all, it is water as a reaction component, but since water is much less reactive than DETDA as described above, it is possible to extend the pot life by replacing part of DETDA with water, but strength development Property and curability will decrease.
When considered under the condition that the NCO content is constant, the addition amount of water as a reaction component reduces the amount of DETDA having high coagulability, so that the final strength is lowered and at the same time, the strength development is delayed. However, there is a limit in covering even if a moisture curing accelerator is used.
Therefore, it is not necessary to mix water as a reaction component.
Regarding the water adhering to the filler mixed with the curing agent, it substantially reacts gently with an excess of isocyanate groups and partially contributes to the increase in the final strength. It is not necessary to consider it as an ingredient.
However, a small amount of water can be added for the purpose of adjusting the amount of water in the curing agent. In the production of a curing agent during drying such as in winter, the amount of water adhered to the filler is small and the moisture involved in the production is small, so the amount of water in the curing agent may be small. In such a case, moisture curing can be facilitated by adding a small amount of water.

Next, it is a method of blending a polyol. Generally, since polyols have a larger molecular weight than water and tend to have low reactivity and low agglomeration, strength development and curability are deteriorated by using them in combination. , But also tends to lower the final strength, but a small amount can be used in combination with an aromatic polyamine.

As a polyol that can be used as a reaction component, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,6 from the viewpoint of high strength. -Hexanediol, 3-methyl-1,5-pentanediol, short-chain polyols such as ethylene glycol, diethylene glycol, dipropylene glycol and tripropylene glycol, polyester polyols and polycarbonate polyols having a relatively high cohesive property are preferable.
Among them, the primary hydroxyl group polyol is more preferable because it is highly reactive and does not easily remain unreacted. Among them, 1,3-propanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, and An aromatic-containing polyester polyol having a molecular weight of 300 to 800 is more preferable for high strength.
The aromatic polyester polyol is preferably a liquid product using a low crystalline polyol such as Kurapol (manufactured by Kuraray Co., Ltd.).
Further, polyoxypropylene polyol or polyoxyethylene propylene polyol having a molecular weight of 1500 or more has a low cohesive property, so that it is not preferable to blend it from the viewpoint of high strength.
When a polyol is used in combination as a reaction component of the curing agent, an organic stannic compound capable of accelerating moisture curing and urethanization reaction at the same time, an imidazole compound having a substituent at the 1- and 2-positions, and a carboxylic acid It is preferable to use a metal salt or the like as a catalyst.

As described above, in the present invention, a polyol or water is not essential as a reaction component, but a small amount of polyol or water is intentionally blended in order to adjust the pot life or the curing time or finely adjust other performances. You can also do it.
In that case, it is necessary that more than 90 equivalent% of all reaction components (aromatic amino group, hydroxyl group of polyol, water) be the aromatic amino group of the aromatic polyamine containing DETDA as the main component. It is more preferably 92 equivalent% or more, further preferably 95 equivalent% or more, and most preferably 100 equivalent%.

(Aromatic polyamine)
In the present invention, it is preferable to use DETDA as a main component as the aromatic polyamine that can be used as the reaction component of the curing agent, but it is also possible to use other aromatic polyamines in combination.
Generally, DETDA has isomers such as 3,5-diethyl-2,4-toluenediamine and 3,5-diethyl-2,6-toluenediamine, but in the present invention, any isomer is present. May be used, or a mixture thereof may be used. Those having different isomer contents are commercially available, and industrial products such as "Etacure 100" (weight ratio of 2,4-isomer/2,6-isomer 80/20) are available.

As the aromatic polyamine which can be used in combination with DETDA, 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, Nippon Kayaku Co., Ltd. Kayahard AA (4,4'-methylenebis(2-ethylaniline) manufactured by K.K., Kayabond C-300 (4,4'-methylenebis(2,6-diethylaniline) manufactured by Nippon Kayaku, Nippon Kayaku) Kayabond C-400 (4,4'-methylenebis(2,6-diiso-propylaniline) manufactured by K.K.
In addition, although it is a low-reactivity aromatic polyamine, Etacure 420 (4,4'-methylenebis(N-sec-butylaniline)) manufactured by Albemarle, Etacure 300 (dimethylthiotoluenediamine) manufactured by Albemarle, etc. are available. Can be used.
DETDA is highly reactive and highly cohesive, and at the same time, it is a liquid having a low viscosity at room temperature, which makes it easy to handle and economically advantageous. Therefore, in the present application, 70 equivalent% or more of the wholly aromatic polyamine is used. Is preferably DETDA, and more preferably 90 equivalent% or more is DETDA.

(Plasticizer)
In this application, the plasticizer plays an important role. Higher strength by IPDI prepolymer and DETDA becomes easier with less plasticizer, but the pot life cannot be secured without the plasticizer. On the other hand, if the amount of the plasticizer is too large, it becomes difficult to increase the strength, and even if the isocyanate content of the main component is increased, the strength cannot be easily increased.
In general, the urethane waterproof material is considered to have an optimal mixture ratio of 1/1 (mass ratio) of the main agent and the curing agent from the viewpoints of ease of measurement at the construction site and prevention of measurement errors. Also in the present application, basically, as a result of studying with a 1/1 mixture, as a result, 16 to 60 parts by mass of the plasticizer is required, and 20 to 50 parts by mass with respect to 100 parts by mass of the prepolymer in the main component. Preferably. If it is 16 parts by mass or less, it is difficult to secure the pot life, and if it is 60 parts by mass or more, it becomes difficult to achieve high strength. When the amount of the plasticizer is within this range, there is no problem in durability performance such as heat resistance and weather resistance, and the waterproof material is excellent in economic efficiency.
The plasticizer is generally added to the curing agent, but a part of the plasticizer may be added to the main agent side, including the plasticizer added to the main agent side, based on 100 parts by mass of the prepolymer in the main agent. It should be 16 to 60 parts by mass.

As the plasticizer, it is possible to use a plasticizer that can be generally mixed with the urethane resin. Examples include phthalates such as diisononyl phthalate (DINP), dioctyl phthalate (DOP), butylbenzyl phthalate (BBP), aliphatic dibasic acid esters, phosphoric acid esters, trimellitic acid esters, sebacic acid esters. Examples thereof include epoxy fatty acid esters, glycol esters, animal and vegetable oil fatty acid esters, petroleum/mineral oil plasticizers, alkylene oxide polymerization plasticizers, and the like.
Of these, diisononyl phthalate (DINP) and dioctyl phthalate (DOP), which have a flash point of 200° C. or higher, are unlikely to cause weight loss over a long period of time, are aromatic polyesters, and are also resistant to hydrolysis, and therefore are preferably used. it can. Although a solvent can be used in the curing agent, there is a risk of contraction due to volatilization after construction and the tendency of the inorganic filler to easily settle, and there is also an environmental problem, so 5% by mass It is preferable to use within, and more preferably not to use. Further, by adding a plasticizer to the curing agent side, it is possible to add a large amount of inorganic filler, and it is possible to provide an economical waterproof material.

(Inorganic filler)
Calcium carbonate is preferred as the inorganic filler. Calcium carbonate has a high economic effect, at the same time has good dispersibility at the time of manufacturing the curing agent, it does not thicken even if it is mixed in a large amount, and it is easy to reduce the sedimentation property when the curing agent is stored. But there are few adverse effects. The calcium carbonate includes various calcium carbonates 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 causes thixotropic properties. It can also be used as a waterproof material for a vertical surface provided with.

Normally used heavy calcium carbonate has about 0.1 to 0.3% by mass of adhered water, but in the present application, it is considered that this adhered water contributes to strengthening, and particularly (isocyanate group/aroma). It is speculated that when the composition of the (group amino group) is 1.05 or more, the strengthening is finally achieved by reacting with the isocyanate group in which the water mainly containing the adhered water is excessively mixed. is doing.
Therefore, in the present invention, it is necessary to mix 20 to 80 mass% of an inorganic filler in the curing agent. By adding an inorganic filler, the amount of water in the curing agent can be adjusted to about 1000 ppm to 2500 ppm, and by adding an inorganic filler that is more hydrophilic than the plasticizer, it is possible to mix two liquids and When a waterproof material is applied and cured and cured, it is possible to easily absorb moisture in the air, and it is possible to support a high strength by moisture curing although it is auxiliary.
When the content of the filler in the curing agent is 20% by mass or less, the effect of supplying water is insufficient, and when it is 80% by mass or more, the workability and physical properties may be deteriorated due to the increased viscosity.
In addition, a filler having attached water such as silica, kaolin, talc, bentonite, aluminum hydroxide or barium hydroxide can be partially used, and in some cases, water can be added.

(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 as required.

(Polyisocyanate)
Next, as the main ingredient, the present application requires that the main component of polyisocyanate is IPDI and the main component of polyol is polyoxyalkyleneine polyol.
IPDI is a low-reactivity polyisocyanate, and it was thought that it was difficult to increase the strength by prepolymer with a low-aggregating polyoxyalkylene polyol, but the reaction used as a curing agent It has been found that when the main component of the components is DETDA, it becomes a material suitable for strengthening and it is easy to secure the pot life. In the present application, more than 70 equivalent% of the polyisocyanate component is preferably IPDI, more preferably 75 equivalent% or more. On the other hand, bifunctional derivatives such as IPDI nurates and ducts have also been commercialized, but many cannot be used because they tend to restrict the elongation, and 0 to 30 equivalent% of all polyisocyanate components are used. It is preferable to use the above range.

In the present invention, a polyisocyanate other than IPDI may be used in combination as the polyisocyanate. As the polyisocyanate that can be used in combination, mildly reactive, aliphatic or alicyclic polyisocyanate is preferable, hexamethylene diisocyanate, norbornene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate. Examples thereof include isocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tetramethylxylylene diisocyanate, and the like.
Further, some aromatic polyisocyanates such as tolylene diisocyanate, xylylene diisocyanate, and tetramethyl xylylene diisocyanate can also be used, but tolylene diisocyanate is a specific chemical substance of the Occupational Safety and Health Act, Not environmentally friendly.

(Main agent NCO content and NCO group/OH group equivalent ratio)
In the present application, the NCO content of the main agent needs to be more than 3.0% by mass and 6.0% by mass or less. In the range of the amount of the plasticizer of the present invention, the strength cannot be increased unless the NCO content exceeds 3.0% by mass. On the other hand, when the NCO content exceeds 6.0% by mass, the amount of DETDA, which is the main component of the reaction components, also increases, and the pot life is shortened, causing a problem in workability. Furthermore, in order to achieve high strength and ensure good workability, the NCO content of the main agent is preferably 3.3 to 5.5 mass %.
The equivalent ratio of the NCO group of the IPDI prepolymer and the OH group of the polyol in the main agent (NCO group/OH group) is preferably 1.5 to 2.5, and 1.6 to 2.3. Is more preferable. When it is less than 1.5, thickening of the main component becomes severe, and when it exceeds 2.5, the amount of free IPDI increases, so that problems such as reduction in elongation and shortening of pot life are likely to occur.

(Primary polyol)
As the polyol component to be reacted with the polyisocyanate, it is necessary that the polyoxyalkylene polyol is the main component, and further, the polyoxypropylene polyol and the polyoxyethylene propylene which have low crystallinity and low viscosity and are excellent in economical efficiency. It is preferably a polyol.
There is also a method of using a polyester polyol having high cohesiveness to increase the strength, but since the polyester polyol is highly viscous, the prepolymer also becomes highly viscous, so that when taking out from the can, mixing the two liquids and applying. Workability deteriorates. Therefore, a large amount of solvent is required to improve workability, but problems such as environmental pollution due to the solvent and cracking or peeling due to shrinkage of the cured product occur.

Furthermore, although general aliphatic polyester polyols are excellent in weather resistance and heat resistance, they are recognized to have problems in hydrolysis resistance, alkali resistance, and bacteria resistance. Not suitable for waterproofing applications.
On the other hand, since the polyoxyalkylene polyol, which is a polyether, has a low cohesive property, the prepolymer also has a relatively low viscosity and can be applied even when the amount of the solvent is 5% by mass or less. Further, since polyether polyol has excellent hydrolysis resistance, alkali resistance, and bacteria resistance, it is suitable for use as a high-strength urethane waterproof material. The polyoxyalkylene polyol is preferably more than 50 equivalent% in the polyol.

(Molecular weight and number of functional groups of base polyol)
In the present application, the elongation rate plays an important role in efficiently increasing the strength, and by ensuring the elongation rate, not only the tensile product but also the tensile strength can be efficiently increased. On the other hand, if an attempt is made to increase the strength without securing the elongation, the hardness will be extremely high (high modulus), and the material will not look like a urethane waterproof material.
Therefore, it is necessary to use 10 to 97 equivalent% of a diol having a molecular weight of 1500 or more as the polyol used as the main component in order to secure the elongation, and it is preferable to use 20 to 80 equivalent%. When 100 equivalent% of the diol having a molecular weight of 1500 or more is used, the division point in the cured product disappears and the concentration of urethane bond also decreases, so that the strength development property and the curability are decreased, and further the final strength is decreased.
In order to solve this problem, it is necessary to use a diol having a molecular weight of less than 1500 or a polyol having a functional group number of 3 or more in an amount of 3 to 90 equivalent %, preferably 20 to 80 equivalent %.
By using a diol having a molecular weight of less than 1,500, the concentration of urethane bond and urea bond in the cured product is increased, so that the strength can be increased without significantly impairing the elongation. Further, by using a polyol having a functional group number of 3 or more, a branch point can be formed in the cured product, so that strength development and curability can be improved, and high strength can be easily achieved.

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 which have low crystallinity and low viscosity, and a special diol is used. You don't have to.
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 it is possible to increase the NCO content without significantly increasing the viscosity of the main agent. Therefore, it is possible to achieve high strength without significantly impairing the elongation.

A polyether polyol having a molecular weight of 200 to 800, in which bisphenol A is used as the initiator, has a high cohesive force among the polyethers and is effective for increasing the strength, and thus can be more preferably used. Further, among the polyester polyols, for example, a low crystalline aroma having a molecular weight of 300 to 800 using an amorphous 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 cohesion.
Further, 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 glycol, diethylene glycol, dipropylene glycol, and tripropylene glycol, can also be used, but if the amount used is too large, the elongation tends to be restricted and the high strength tends to be hindered. It is preferably less than 50 equivalent %.

As the polyol having 3 or more functional groups, a polyoxyalkylene triol having a molecular weight of 1500 or more can be used, and general polyoxypropylene triol or polyoxyethylene propylene triol is preferable.
A polyoxypropylene polyol or a polyoxyethylene propylene polyol having a functional group number of 4 or more tends to restrain the elongation rate, and therefore a small amount can be used.
A polyoxyalkylene triol having a molecular weight of less than 1500 can also be used, and polyoxypropylene triol or polyoxyethylene propylene triol is preferable, but again, since the tendency to restrain the elongation is strong, 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 tend to restrain the elongation rate, and thus can be used only in a small amount.

(Synthesis of prepolymer)
Although this is a method of synthesizing an IPDI prepolymer, it is preferable to use a catalyst because the reaction is difficult to accelerate by simply heating. Although a general urethanization catalyst can be used, an organic stannic tin catalyst such as DBTDL or DOTDL is preferable, and the reaction can be efficiently promoted with a small addition amount of 0.0001 to 0.1% by mass. ..
The reaction temperature is preferably 60°C to 110°C, and the reaction can be completed in about 2 to 10 hours. After the reaction is completed, it is preferable to deactivate the catalyst with phosphoric acid or the like.

(Main agent/Curing agent mix ratio)
The mixing ratio of the main agent and the curing agent is preferably 1/1 in terms of mass ratio. In some cases, it is divided into small pieces at the construction site and weighed. When the mixing ratio is 1/1, there are few weighing errors.
However, when a thixotropic agent such as colloidal calcium carbonate is added to the curing agent side to form a waterproofing material for rising, a large amount of filler is required, and therefore more than 1/1 to 1/2 and many curing agents are used. It may be a combination of

(Waterproofing composition)
Since the purpose of the present application is waterproofing of a foundation such as a concrete foundation that cracks over time, emphasis is placed on ensuring the elongation required for crack followability. Therefore, in the present application, the elongation rate is 200% or more according to the JIS standard of the high-strength urethane waterproof material, while the elongation rate is preferably 300% or more, and more preferably 450% or more.
As a result, the tensile strength is remarkably higher than that of the conventional waterproof material, and the waterproof material is less likely to be broken even without the reinforcing cloth. Therefore, it is possible to use without using the reinforcing mesh. For large-scale rooftop waterproofing, the ventilation cushioning method that deaerates moisture (moisture) in the foundation concrete is good as before, but it is a small area construction or rising part, eaves part, accessory part, gutter part. Even when a reinforcing cloth (mesh) is not inserted, the waterproof performance can be exerted in the construction of the portion where the construction is troublesome, and a significant labor saving can be achieved.

(Waterproof method)
The high-strength urethane waterproof material of the present application cannot be applied directly to an inorganic base such as concrete. In the case of an inorganic base, since it does not adhere to the high-strength urethane waterproof material, it is necessary to apply it after applying a primer capable of shielding the base moisture and ensuring adhesiveness.
In addition, in both new construction and renovation work, various ventilation cushioning sheets, polymer sheets using vinyl chloride or vulcanized rubber, root coating sheets, polymer coatings such as epoxy resin and FRP are not directly applied to the inorganic base. It is possible to apply a primer on the membrane material and, if necessary, apply the primer and then apply the primer.
Further, even in the case of a metal base, even if the high-strength urethane waterproof material of the present application is directly applied, the adhesiveness cannot be secured, so that it can be applied after applying a dedicated primer.

After applying a primer to an inorganic base, etc., apply a conventional low-strength, high-strength two-component waterproof material or one-component waterproof material, and then apply the high-strength waterproof material of the present application on it. You can
By constructing a two-layer structure with different hardness in this way, the low hardness part of the lower layer serves to buffer the movement of cracks that occur in the base, and the upper layer has a high hardness part with high elongation and high strength. Therefore, it is possible to construct a waterproof layer that does not break without using a reinforcing cloth. Moreover, after applying the high-strength waterproof material of the present application, a polymeric waterproof material such as vinyl chloride, a root-proof sheet, a non-slip material, and various molded articles can be installed.
The present invention is not intended to repair an asphalt-based waterproof layer, and is intended to waterproof and protect an inorganic substrate such as concrete, a metal substrate, a polymer resin sheet substrate, and a polymer coating material substrate. It is a thing.

(Top coat)
In addition, the high-strength urethane waterproof material of the present application is, in principle, applied with a top coat when it is used in a portion exposed to direct sunlight. However, topcoat application is not required when used in areas not exposed to sunlight, such as rooftop greening and civil engineering applications.

Raw Materials The raw materials used in the following Examples and Comparative Examples are as follows.
IPDI: VESTANAT (registered trademark) IPDI, isophorone diisocyanate simple substance, NCO content of 37.8 mass%, NCO functional group number of about 2.0, manufactured by Evonik Japan KK Sannix PP-2000: polyoxypropylene diol, average Molecular weight 2000, OH value 56.1 mgKOH/g, Sanyo Chemical Industry Co., Ltd. Sannix GH-3000: Polyoxypropylene triol, average molecular weight 3000, OH value: 56.1 mgKOH/g, Sanyo Chemical Co., Ltd. Newpol BP -5P: Polyoxypropylene diol, average molecular weight 500, OH value: 209 mgKOH/g, Sanyo Kasei Co., Ltd. MC-2000 solvent: Normal paraffin, isoparaffin mixture, Sankyo Chemical Co., Ltd. Dioctyltin dilaurate: KS-1200A- 1, manufactured by Kyodo Pharmaceutical Co., Ltd. DETDA: Ethacure 100, diethyltoluenediamine, Albemarle Japan Co., Ltd. DINP: Sanso Sizer DINP, diisononyl phthalate, Shin Nippon Rika Co., Ltd. calcium carbonate NS#100: NS#100, calcium carbonate, Nitto Powder Industry Co., Ltd. Additives: Kusumoto Kasei Co., Ltd. Calcium Carbonate Calfine N-2: Calcium Carbonate (Surface Treatment), Maruo Calcium Co., Ltd. T-80: Coronate T-80, 2,4-Tolylene Diene Isocyanate/2,6-tolylene diisocyanate=80/20 (mass ratio) mixture, NCO content 48.3% by mass, manufactured by Tosoh Corporation T-100: Coronate T-100, 2,4-tolylenediene. 100% isocyanate-containing product, NCO content 48.3% by mass, manufactured by Tosoh Corporation Sannix GH-5000: polyoxypropylene triol, average molecular weight 5000, OH value: 33.7 mg KOH/g, manufactured by Sanyo Chemical Industry Co., Ltd. Etacure 420: 4,4'-methylenebis(N-sec-butylaniline), aromatic secondary diamine, Albemarle Kuraray Polyol P-530: by reaction of 3-methyl-1,5-pentanediol and isophthalic acid. Aromatic polyester diol obtained, average molecular weight 500, OH value: 224.4 mg KOH/g, Kuraray Co., Ltd. 2-ethylhexyl acid: octylic acid, Toyo Gosei Co., Ltd. 1-isobutyl-2-methylimidazole: DABCO NC -IM, Airp Rodactu Japan Co., Ltd. dibutyltin dilaurate: KS-1260, Kyodo Chemical Co., Ltd. 2-ethylhexylate lead (Pb 20%): Nikka Octix lead 20% TS, 2-ethylhexylate lead and normal paraffin, isoparaffin mixture Mixture, containing 20% as Pb, Nikka Octix Zn 8%T manufactured by Nippon Kagaku Sangyo Co., Ltd.: Nikka Octix zinc 8% (T), a mixture of zinc 2-ethylhexylate and mineral spirits, containing 8% Zn. Nippon Kagaku Sangyo Co., Ltd. Nikka Octix Ca 5% TK: Nikka Octix calcium 5% (TK), a mixture of 2-ethylhexylate calcium and an isoparaffinic solvent, 5% as Ca, Tetrahydro by Nippon Kagaku Sangyo Co., Ltd. Methyl phthalic anhydride: HN-2200R, tetrahydromethyl phthalic anhydride, manufactured by Hitachi Chemical Co., Ltd. Sannix FA-703: ethylene oxide-added polyoxypropylene triol, average molecular weight 5000, OH value: 33 mg KOH/g, Sanyo Chemical Industrial Co., Ltd. Company 1,4-butanediol: Reagent, Nacalai Tesque, Inc. 2-Methyl-1,3-propanediol: MPDiol Glycol, Kuraray Trading Co., Ltd. Sannix PP-1000: Polyoxypropylene diol, average molecular weight 1000, OH number 112.2 mgKOH/g, Sanyo Chemical Industry Co., Ltd. Sannix PP-400: Polyoxypropylene diol, average molecular weight 400, OH value 280.5 mgKOH/g, Sanyo Chemical Industry Co., Ltd.

Preparation of Main Agent According to the formulations shown in Tables 1 to 14, a four-necked flask was charged with a polyol, a solvent, and if necessary, dioctyltin dilaurate, and then a polyisocyanate compound. Then, each mixture was reacted with stirring at 90 to 100° C. for 3 to 7 hours to obtain each main agent. In Example 16, tetrahydromethylphthalic anhydride was added in accordance with the blending amount shown in Table 5 after the main agent was synthesized and cooled.

Preparation of Hardening Agent According to the formulations shown in Tables 1 to 11, the liquid material was charged into a metal container and mixed at a low speed with a stirrer (dissolver blade) to homogenize, and then calcium carbonate was added and mixed at 1500 rpm for 15 minutes to obtain each curing agent. Obtained.

Examples 1-6 (Table 1), Comparative Examples 1-2 (Table 2)
In Examples 1 to 6, according to the formulation of Table 1, in Comparative Examples 1 and 2, the main agent and the curing agent were obtained according to the formulation of Table 2. A urethane waterproof material composition was obtained by mixing these main ingredients and a curing agent in a mass ratio of 1:1.
Example 1 in which the main agent NCO/hardener NH ₂ (equivalent ratio) is 0.95, Example 2 in 1.00, Example 3 in 1.05, Example 4 in 1.07, Example in 1.10. Examples 5 and 1.20 of Example 6 showed good coating properties as a high-strength urethane waterproof material for hand-coating and could be applied the next day while ensuring a sufficient pot life. Comparative Example 1 in which the main agent NCO/hardening agent NH ₂ (equivalent ratio) was 1.30 and Comparative Example _{2 in which the} ratio was 0.90 were not good in coating film physical properties.

Comparative Examples 3-5 (Table 2)
In Comparative Examples 3 to 5, according to the formulations shown in Table 2, a main agent and a curing agent were obtained. A urethane waterproof material composition was obtained by mixing these main components and a curing agent in a mass ratio of 1:2.
Comparative example 3 in which T-80 was used as the main component polyisocyanate compound and the main component NCO/hardening agent NH ₂ (equivalent ratio) was 0.90, comparative example 4 of 1.05, and comparative example 5 of 1.20 were However, the physical properties of the coating film were not good.

Comparative Examples 6 to 7 (Table 2)
In Comparative Examples 6 to 7, the main agent and the curing agent were obtained according to the formulations shown in Table 2. A urethane waterproof material composition was obtained by mixing these main ingredients and a curing agent in a mass ratio of 1:1.
Comparative Example 6 in which T-100 was used as the base polyisocyanate compound and GH-5000 was used as the triol/Comparative NCO/hardening agent NH ₂ (equivalent ratio)=1.20, T-100 was used as the main polyisocyanate compound, Comparative Example 7 in which GH-3000 was used as the triol, the main agent NCO/hardening agent NH ₂ (equivalent ratio)=1.20 was not good in coating film physical properties and had a short pot life.

Examples 7 to 14 (Tables 3 and 4)
In Examples 7 to 14, a main agent and a curing agent were obtained according to the formulations shown in Tables 3 and 4. This base material and the curing agent were mixed at a mass ratio of 1:1 to obtain a urethane waterproof material composition.
Example 7 using 0.30% by mass of 2-ethylhexylic acid as a curing accelerator in the curing agent, Example 8 using 0.30% by mass of 1-isobutyl-2-methylimidazole, 1-isobutyl-2-methyl Example 9 using 0.50% by mass of imidazole, Example 10 using 0.05% by mass of dibutyltin dilaurate, Example 11 using 0.10% by mass of dibutyltin dilaurate, lead 2-ethylhexylate (Pb20). %) of 0.50% by mass, Example 13 using Nikka octix Zn8% T of 1.32% by mass, and Example 14 using 1.30% of Nikka octix Ca of 5% TK are used. As a high-strength urethane waterproof material for hand-painting, it showed good coating properties and could be applied the next day while ensuring a sufficient pot life.

Examples 15 to 17 (Table 5)
In Examples 15 to 17, the main agent and the curing agent were obtained according to the formulations shown in Table 5. This base material and the curing agent were mixed at a mass ratio of 1:1 to obtain a urethane waterproof material composition.
As a curing accelerator for an acid anhydride, Example 15 in which tetrahydromethylphthalic anhydride was added to the curing agent in an amount of 0.30% by mass, Example 16 in which tetrahydromethylphthalic anhydride was added to the main component in an amount of 0.30% by mass, and Example 17 in which 0.30% by mass of tetrahydromethylphthalic anhydride was added to a mixture of a main agent and a curing agent showed good coating properties as a high strength urethane waterproof material for hand-coating and had a sufficient pot life. It was possible to construct the next day while securing

Example 18, Comparative Examples 8-10 (Table 6)
In Example 18 and Comparative Examples 8 to 10, the main agent and the curing agent were obtained according to the formulations in Table 6. This base material and the curing agent were mixed at a mass ratio of 1:1 to obtain a urethane waterproof material composition.
Example 18 in which water as an active hydrogen compound was not added to the curing agent exhibited good coating properties as a high-strength urethane waterproof material for hand-coating and could be applied on the next day while ensuring a sufficient pot life. It was Comparative example 8 in which water as an active hydrogen compound was added to the curing agent so that DETDA/water (equivalent ratio) was 90/10, and comparative example 9 and 80/20 were added in such a manner that 85/15 was added. In Comparative Example 10 thus added, the coating film physical properties and heat resistance were not good.

Example 19, Comparative Example 11, Example 20 (Table 7)
In Example 19, Comparative Example 11, and Example 20, the main agent and the curing agent were obtained according to the formulations in Table 7. This base material and the curing agent were mixed at a mass ratio of 1:1 to obtain a urethane waterproof material composition.
Using 1.01% by mass of Kuraray Polyol P-530 as a curing agent, DETDA (equivalent%) in the aromatic polyamine of the curing agent is 100, aromatic polyamine/other active hydrogen (equivalent ratio) is 95/5, Example 19 in which the main agent NCO/hardener NH ₂ (equivalent ratio) was 1.11, 0.97% by mass of Etacure 420 was used as the hardener, and DETDA (equivalent%) in the aromatic polyamine of the hardener was 95, Example 20 having an aromatic polyamine/other active hydrogen (equivalent ratio) of 100/0 and a main agent NCO/hardening agent NH ₂ (equivalent ratio) of 1.05 is suitable as a high strength type urethane waterproof material for hand coating. It could be applied the next day while showing the physical properties of the coating film and ensuring a sufficient pot life. Using 24.56% by mass of Sannix FA-703 as a curing agent, DETDA (equivalent%) in the aromatic polyamine of the curing agent is 100, aromatic polyamine/other active hydrogen (equivalent ratio) is 82/18, In Comparative Example 11 in which the main agent NCO/hardener NH ₂ (equivalent ratio) was 1.28, the coating film physical properties were not good.

Examples 21-22 (Table 8)
In Examples 21 to 22, a main agent and a curing agent were obtained according to the formulations shown in Table 8. This base material and the curing agent were mixed at a mass ratio of 1:1 to obtain a urethane waterproof material composition.
Example 21 in which 35.00% by mass of DINP was used as the curing agent in the curing agent, and Example 22 in which 40.00% by mass of the DINP was used in the curing agent showed good coating film physical properties as a high-strength urethane waterproof material for hand-coating, and sufficient It was possible to carry out construction the next day while ensuring sufficient pot life.

Examples 23-25 (Table 9)
In Examples 23 to 25, the main agent and the curing agent were obtained according to the formulations shown in Table 9. A urethane waterproof material composition was obtained by mixing these main ingredients and a curing agent in a mass ratio of 1:1.
Example 23 in which the main agent had an NCO/OH (equivalent ratio) of 2.10 and an NCO content of 4.81% by mass. The main agent had an NCO/OH (equivalent ratio) of 2.00 and an NCO content of 4.40 mass. % Of Example 24, NCO/OH (equivalent ratio) of the main agent is 1.90, and Example 25 with an NCO content of 3.93 mass% is a coating film having good coating physical properties as a high strength type urethane waterproof material for hand coating. It was possible to carry out the construction the next day while showing the above and ensuring a sufficient pot life.

Comparative Example 12, Examples 26 to 34 (Tables 10 and 11)
In Comparative Example 12 and Examples 26 to 34, a main agent and a curing agent were obtained according to the formulations of Tables 10 and 11. A urethane waterproof material composition was obtained by mixing these main ingredients and a curing agent in a mass ratio of 1:1.
In Comparative Example 12 in which only Sannix PP-2000 was used as the main component polyol, the coating film physical properties were not good.
Example 26 in which Sannix PP-2000/Sannix GH-3000=80/20 (equivalent ratio) was used as a main component as a polyol, and Sannix PP-2000/Newpol BP-5P=50/50(as a main component as a polyol) Example 27 using an equivalent ratio), Example 28 using Sannix PP-2000/Newpol BP-5P/Sannix GH-3000=50/45/5 (equivalent ratio) as a polyol in the main component, the main component Example 29 using Sannix PP-2000/Newpol BP-5P/Sannix GH-3000=40/50/10 (equivalent ratio) as the polyol, Sannix PP-2000/Newpol BP- as the main component polyol. Example 30 using 5P/Sannix GH-3000=40/40/20 (equivalent ratio), Sannix PP-2000/Newpol BP-5P/Sannix GH-3000=40/30/ as a main component with a polyol Example 31 using 30 (equivalent ratio), Example 32 using Sannix PP-2000/Newpol BP-5P/Sannix GH-3000=30/60/10 (equivalent ratio) as a polyol as the main component, Example 33 in which Sannix PP-2000/Newpol BP-5P/Sannix GH-3000=30/50/20 (equivalent ratio) was used as a main component as a polyol, and Sannix PP-2000/Newpall was used as a main component as a polyol. Example 34 using BP-5P/Sannix GH-3000=20/60/20 (equivalent ratio) shows good coating physical properties as a high-strength urethane waterproof material for hand coating and has a sufficient pot life. It was possible to construct the next day while securing

Examples 35-40 (Table 12)
In Examples 35 to 40, a main agent and a curing agent were obtained according to the formulations shown in Table 12. A urethane waterproof material composition was obtained by mixing these main ingredients and a curing agent in a mass ratio of 1:1.
Example 35 in which Sannix BP-5P was used as the main agent as a diol having an average molecular weight of less than 1500, Example 36 in which 1,4-butanediol was used, and Example 37 in which 2-methyl-1,3-propanediol was used. , Example 38 using Kuraray Polyol P-530, Example 39 using Sannix PP-1000, and Example 40 using Sannix PP-400 are good as a urethane waterproof material for high strength type hand coating. It could be applied the next day while showing the physical properties of the coating film and ensuring a sufficient pot life.

Examples 41-42 (Table 13)
In Examples 41 to 42, a main agent and a curing agent were obtained according to the formulations shown in Table 13. A urethane waterproof material composition was obtained by mixing these main ingredients and a curing agent in a mass ratio of 1:1.
Example 41 using Sannix GH-3000 having an average molecular weight of 3000 as the main agent as a triol, and Example 42 using Sannix GH-5000 having an average molecular weight of 5000 are good coatings as a urethane waterproof material for high strength hand coating. It was possible to construct the next day while showing the physical properties of the film and ensuring a sufficient pot life.

Example 43 (Table 14)
In Example 43, a main agent and a curing agent were obtained according to the formulations shown in Table 14. A urethane waterproof material composition was obtained by mixing these main ingredients and a curing agent in a mass ratio of 1:1.
Example 43, in which the surface-treated calcium carbonate Calfine N-2 was used as the curing agent, had high thixotropy and exhibited good coating film physical properties as a high-strength type urethane waterproof material for hand-coating which requires anti-dripping property. Construction was possible the next day while ensuring sufficient pot life.

The measuring method of each evaluation item is as follows.

[NCO (mass %)]
About 1 g of the main ingredient is precisely weighed in a 200 mL Erlenmeyer flask, 10 mL of 0.5N di-n-butylamine (toluene solution), 10 mL of toluene and an appropriate amount of bromphenol blue are added, and then about 100 mL of methanol is added and dissolved. 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)*4.202*0.25N hydrochloric acid solution factor*0.25/sample weight

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

[Constructable time (hours)]
In an air-circulation type environmental test room with a temperature of 23°C and a humidity of 50%, 2 kg/m ^{2 of} a waterproof material prepared by agitating and mixing a main agent and a curing agent at a predetermined ratio was applied. The time during which walking was possible and the work of the next process could be started was measured.

[Curing time (hours)]
2 kg/m ^{2 of} a waterproof material obtained by stirring and mixing a main agent and a curing agent at a predetermined ratio was applied in an air circulation type environmental test chamber at 23° C. and a humidity of 50%, and the time until complete curing was measured.

[Tensile strength (N/mm ² )]
Measurements were performed based on JIS A 6021 for test pieces whose curing conditions were 7 days at 23° C., 14 days at 23° C., and 28 days at 23° C. (7 days or more at 23° C. in JIS A 6021) (JIS A 6021). The tensile strength of the A6021 urethane rubber high strength type is 10 N/mm ² or more).

[Elongation at break (%)]
Measurements were performed based on JIS A 6021 for test pieces whose curing conditions were 7 days at 23° C., 14 days at 23° C., and 28 days at 23° C. (7 days or more at 23° C. in JIS A 6021) (JIS A 6021). A6021 urethane rubber high elongation type (former type 1) has an elongation at break of 450% or more).

[Tear strength (N/mm)]
Measurements were performed based on JIS A 6021 for test pieces whose curing conditions were 7 days at 23° C., 14 days at 23° C., and 28 days at 23° C. (7 days or more at 23° C. in JIS A 6021) (JIS A 6021). The tear strength is 30 N/mm or more in the urethane rubber type high strength type of A6021).

[Tensile product (N/mm)]
Using a tensile strength and an elongation at break for a test piece whose curing conditions were 7 days at 23° C., 14 days at 23° C. and 28 days at 23° C. (7 days or more at 23° C. in JIS A6021), Calculation was performed based on JIS A 6021 (tensile product is 700 N/mm or more in the urethane rubber high strength type of JIS A 6021).

[Hardness (Durometer)]
Measurements were carried out according to JIS K 7312 for test pieces whose curing conditions were 23° C. for 7 days, 23° C. for 14 days, and 23° C. for 28 days.

[Heat resistance Tensile strength ratio (%) and elongation at break (%)]
A test piece heat-treated by being put in a dryer at 80°C for 28 days (80 days at 80°C in JIS A 6021) was tested according to JIS A 6021. The elongation rate (%) was calculated.

INDUSTRIAL APPLICABILITY The composition of the present invention can be suitably used as a high-strength, two-component environment-friendly hand-painted urethane waterproof material for waterproofing roofs of buildings or balconies of collective housing such as condominiums.

Claims (7)

Two-component environment-friendly urethane waterproof material for hand-coating, which comprises a main agent containing an isocyanate group-terminated prepolymer composed of polyisocyanate and polyol, and a curing agent containing an aromatic polyamine as a reaction component, a plasticizer and an inorganic filler. A composition,
a) The main component polyisocyanate contains isophorone diisocyanate, more than 70 equivalent% of the polyisocyanate is isophorone diisocyanate, the main component polyol contains a polyoxyalkylene polyol, and the main component polyol has a molecular weight of 1500 or more. 10 to 97 equivalent% of diol and 3 to 90 equivalent% of a diol having a molecular weight of less than 1500 or a polyol having a functional group of 3 or more (in the case where the base polyol contains a diol having a molecular weight of less than 1500 and a polyol having a functional group of 3 or more, the molecular weight is A diol of less than 1500 and a polyol having a functional number of 3 or more in total of 3 to 90 equivalent %), and the isocyanate group-terminated prepolymer has an NCO content of more than 3.0% by mass and 6.0% by mass or less,
b) The curing agent has an aromatic polyamine in an amount of more than 90 equivalent% in all reaction components, the aromatic polyamine contains diethyltoluenediamine, and the inorganic filler contains 20 to 80% by mass.
c) The plasticizer is blended with the curing agent, or divided into both the main agent and the curing agent, so as to be 16 to 60 parts by weight with respect to 100 parts by weight of the prepolymer in the main agent,
Two-component environment-friendly, with an equivalent ratio (isocyanate group/aromatic amino group) between the isocyanate group of the main agent and the amino group of the aromatic polyamine that is the reaction component in the curing agent is 0.92 to 1.24. Urethane waterproofing material composition for hand coating. At least one selected from the group consisting of an organic stannic compound, a carboxylic acid metal 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 environment-friendly hand-coating urethane waterproof material composition according to claim 1, which contains a seed. The two-component environment-friendly hand-coating urethane waterproof material composition according to claim 1 or 2, wherein an organic stannic tin 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. 50 equivalent% of base resin of the polyol is a polyoxyalkylene polyol, 2-part environmental hand-painted urethane waterproofing material composition according to any one of claims 1-3. 70 equivalent percent of the aromatic polyamine is diethyl toluenediamine, 2-part environmental hand-painted urethane waterproofing material composition according to any one of claims 1-4. To an adherend, was subjected to primer layer, or after applying a primer layer and a urethane waterproof material layer, two-environmental hand-painted urethane waterproof material according to any one of claims 1 to 5 A urethane waterproofing method including a step of applying a composition. To adherends, aeration buffer sheet, polymer sheet, after having been subjected to Bone sheet or polymeric coating material, for two-environmental hand-painted according to any one of claims 1 to 5 A urethane waterproofing method including a step of applying a urethane waterproofing material composition.