Two-component urethane waterproofing material composition for hand application and method for applying urethane waterproof coating layer

Abstract

To provide a two-liquid type urethane water-proof material composition for hand coating, which shows sufficient hardness as a finishing material for a sports floor and a parking area and can ensure a sufficient pot life throughout the year.SOLUTION: A two-liquid type urethane water-proof material composition for hand coating comprises: a main agent comprising a prepolymer with terminal isocyanate groups, the prepolymer comprising a polyisocyanate and a polyol; and a curing agent comprising an aromatic polyamine and an inorganic filler, where more than 70 equivalent% of the polyisocyanate is accounted IPDI, the NCO content of the main agent is 3.0-6.0 mass%, the curing agent comprises 20-80 mass% of the inorganic filler, more than 80 equivalent% of all reactive components in the curing agent is an aromatic polyamine, more than 70 equivalent% of the aromatic polyamine is DETDA, 3-25 pts.mass of a plasticizer relative to 100 pts.mass of the prepolymer is blended into the curing agent or separately into both of the main agent and the curing agent, 10-40 mass% of a solvent relative to the composition is blended into the curing agent or separately into both of the main agent and the curing agent, the solvent comprises more than 30 mass % of an aprotic solvent having a solubility parameter of 8.0-14.0, and a ratio of the amount (milli equivalent) of amino groups in the aromatic polyamine relative to the amount (g) of the plasticizer is 4.0-45.0.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a two-component urethane waterproofing material composition for hand application and a method for applying a urethane waterproof coating layer for sports floors and parking lots. [Background technology]

[0002] Because polyurethane waterproofing materials are suitable for application in irregularly shaped and confined spaces, they have been widely used for waterproofing balconies and eaves of apartment buildings and other multi-unit dwellings, as well as for waterproofing rooftops with many fittings, and even for full-scale rooftop waterproofing using breathable buffer sheets. On the other hand, for areas subjected to heavy loads such as sports floors and rooftop parking lots, a high-hardness polyurethane coating waterproof layer with excellent elasticity and rigidity is required as a finishing material.

[0003] Currently used urethane waterproofing materials are classified into two types according to JIS A 6021 "Waterproofing Materials for Buildings": high-elongation type and high-strength type. The high-elongation type is a general-purpose waterproofing material for hand application, with an elongation rate at break (hereinafter referred to as "elongation rate") of 450% or more and a tensile strength of 2.3 N / mm². 2 The above specifications stipulate a tensile strength of 280 N / mm² or more, and it is mainly used in non-walk-friendly or light-walk-friendly areas. On the other hand, the high-strength type has an elongation of 200% or more and a tensile strength of 10 N / mm². 2 As described above, the standard specifies a tensile strength of 700 N / mm² or more, and it is often used for special applications such as waterproof flooring for parking lots, root-resistant waterproofing materials for rooftop greening, and waterproofing materials for metal roofs. The main material is an ultra-fast curing urethane material that is spray-applied using a dedicated spray device that impact-mixes two highly reactive components. However, spray application presents a major problem due to the scattering of mist generated during application. It is necessary to carefully protect the area around the application site with film, etc., and also to pay attention to nearby houses and cars, making it unsuitable for application in densely populated residential areas. In addition, the spray device is expensive and requires a dedicated technician, which limits the number of contractors that can perform the application. JIS A 6021 does not specify hardness, but the JIS D hardness of a typical spray coating using ultra-fast curing urethane material is around 35-45.

[0004] Among two-component, hand-applied urethane waterproofing materials that have few application problems, a two-component, environmentally friendly, hand-applied urethane waterproofing material composition (Patent Documents 1 and 2) is known that has a relatively high hardness coating film, in which the main component polyisocyanate contains isophorone diisocyanate (hereinafter referred to as IPDI) and the hardener contains diethyltoluenediamine (hereinafter referred to as DETDA), corresponding to the JIS A 6021 urethane rubber high-strength type. However, the hardness of its cured coating film is at most about 85 on the JIS A hardness scale (equivalent to 33 on the JIS D hardness scale), which is insufficient for sports floors and urethane coating layers for parking lots.

[0005] Two-component, hand-applied urethane waterproofing materials are applied by mixing two liquid components in a mixer and then applying them by hand using a trowel, spatula, roller, brush, etc. After mixing in the mixer, a usable time of at least 30 minutes (hereinafter referred to as the pot life) is required. The above-mentioned two-component urethane waterproofing material for hand application generally comes in two formulations: a summer formulation suitable for application at around 30°C in summer and a winter formulation suitable for application at around 10°C in winter, as the ambient temperature differs significantly between winter and summer application. For example, the summer formulation is designed to have a pot life of 50 minutes or more at 23°C, while the winter formulation is designed to have a pot life of 30 minutes or more at 23°C. Generally, pot life is defined as the time it takes for the viscosity to reach 60,000 to 100,000 mPa·s after mixing the two components at 23°C. Furthermore, it is desirable that the urethane waterproofing material be applied in the evening and hardened enough for light foot traffic by the following morning, and it is considered best if the hardening time can be adjusted to within 17 hours throughout the year.

[0006] Generally, two-component, hand-applied urethane waterproofing materials use plasticizers to ensure sufficient working time throughout the year, as well as high elasticity and hardness. It is relatively easy to increase the resin concentration and thus the hardness of the urethane coating by replacing some of the plasticizer with a solvent that ultimately volatilizes into the air. However, in this case, the reaction between the main component and the hardener is accelerated, making it difficult to ensure a sufficient working time. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2017-43740 [Patent Document 2] Japanese Patent Application Publication No. 10-17819 [Overview of the project] [Problems that the invention aims to solve]

[0008] Conventionally, spray-type ultra-fast-curing polyurethane waterproofing materials, mainly used as finishing materials for sports floors and parking lots, have problems such as the scattering of mist generated during application and the need for a dedicated technician. On the other hand, the formulation technology for two-component, hand-applied polyurethane waterproofing materials has limitations in ensuring sufficient pot life for summer application while maintaining hardness and other properties that are practical for sports floors and parking lots. There has been a demand for a two-component, hand-applied polyurethane waterproofing material composition that maintains sufficient pot life throughout the year and is also durable enough for sports floors and parking lots. [Means for solving the problem]

[0009] In light of these problems, the inventors diligently studied a two-component, hand-applied urethane waterproofing material composition that has sufficient pot life throughout the year, possesses sufficient hardness for use as a finishing material for sports floors and parking lots, and does not require measures to prevent scattering during application or special equipment and dedicated technicians. In a two-component, hand-applied urethane waterproofing material composition comprising a main component containing an isocyanate-terminated prepolymer consisting of polyisocyanate and polyol, a curing agent containing an aromatic polyamine and an inorganic filler, a plasticizer, and a solvent, we have discovered that by using isophorone diisocyanate as the polyisocyanate in the main component, diethyltoluenediamine as the aromatic polyamine in the curing agent, adjusting the ratio of the total amount of plasticizer (g) to the amount of amino groups (milliequivalent) of the aromatic polyamine to a specific range, and further using an aprotic solvent having a specific range of solubility parameters (SP value) as the solvent, we can obtain a two-component, hand-applied urethane waterproofing material composition that has sufficient pot life throughout the year and also has sufficient hardness of a cured coating film for use as a finishing material for sports floors and parking lots, thus completing the present invention.

[0010] The present invention relates to a two-component urethane waterproofing material composition for hand application, comprising a main component containing an isocyanate-terminated prepolymer consisting of a polyisocyanate and a polyol, and a curing agent containing an aromatic polyamine and an inorganic filler. In the main component, more than 70 equivalents of the polyisocyanates constituting the isocyanate-terminated prepolymer are isophorone diisocyanates, and the NCO content of the main component is 3.0% to 6.0% by mass. The curing agent contains 20% to 80% by mass of inorganic filler, and more than 80 equivalents of the total reactive components in the curing agent are aromatic polyamines, and more than 70 equivalents of the aromatic polyamines are diethyltoluenediamine. A plasticizer is added in an amount of 3 to 25 parts by mass per 100 parts by mass of isocyanate-terminated prepolymer in the main component, either separately in the curing agent or in both the main component and the curing agent. The urethane waterproofing material composition contains 10% to 40% by mass of solvent, either in the curing agent or separately in both the main agent and the curing agent, and the solvent contains more than 30% by mass of aprotic solvent with a solubility parameter (SP value) of 8.0 to 14.0. The material is characterized by a ratio of the amount of amino groups (milli-equivalent) of aromatic polyamine to the amount of plasticizer (g) of which is 4.0 to 45.0. The second invention of this case is a method for constructing a urethane waterproof coating layer, which includes mixing and applying a two-component urethane waterproofing material composition for manual coating of the first invention of this case and an inorganic aggregate after applying a primer layer on a base surface, or after applying a primer layer and a urethane waterproofing material layer.

[0011] The present invention includes the following aspects. [1] A two-component urethane waterproofing material composition for manual coating, which consists of a main agent containing an isocyanate group-terminated prepolymer composed of polyisocyanate and polyol, and a curing agent containing an aromatic polyamine and an inorganic filler, More than 70 equivalent % of the polyisocyanate constituting the isocyanate group-terminated prepolymer in the main agent is isophorone diisocyanate, and the NCO content of the main agent is 3.0 mass % to 6.0 mass %, The curing agent contains 20 mass % to 80 mass % of an inorganic filler, more than 80 equivalent % of all reaction components in the curing agent is an aromatic polyamine, and more than 70 equivalent % of the aromatic polyamine is diethyltoluenediamine, 3 parts by mass to 25 parts by mass of a plasticizer is blended into the curing agent, or divided into both the main agent and the curing agent, based on 100 parts by mass of the isocyanate group-terminated prepolymer in the main agent, 10 mass % to 40 mass % of a solvent is blended into the curing agent, or divided into both the main agent and the curing agent, for the urethane waterproofing material composition. The solvent contains more than 30 mass % of an aprotic solvent with a solubility parameter (SP value) of 8.0 to 14.0, A two-component urethane waterproofing material composition for manual coating, where the ratio of the amino group amount (milli-equivalent) of the aromatic polyamine to the amount (g) of the plasticizer is 4.0 to 45.0. [2] The two-component urethane waterproofing material composition for manual coating according to [1], where the polyol constituting the isocyanate group-terminated prepolymer in the main agent contains polyoxyalkylene polyol, and the polyol constituting the isocyanate group-terminated prepolymer in the main agent contains 10 to 97 equivalent % of a diol with a molecular weight of 1500 or more and 3 to 90 equivalent % in total of a diol with a molecular weight of less than 1500 and a polyol with a functionality of 3 or more. [3] The two-component urethane waterproofing material composition for manual application 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 a reaction component in the curing agent is 0.9 to 1.5. [4] The two-component urethane waterproofing material composition for manual application according to any one of [1] to [3], wherein more than 50 equivalent % of the polyol constituting the isocyanate group-terminated prepolymer in the main agent is polyoxyalkylene polyol. [5] The two-component urethane waterproofing material composition for manual application according to any one of [1] to [4], wherein the JIS D hardness of the cured coating film of the urethane waterproofing material composition is 35 to 60. [6] A method for constructing a urethane waterproof coating layer, which includes mixing the two-component urethane waterproofing material composition for manual application according to [1] and an inorganic aggregate after applying a primer layer on the base surface, or after applying a primer layer and a urethane waterproofing material layer, and then applying the mixture.

Advantages of the Invention

[0012] The two-component urethane waterproofing material composition for manual application of the present invention exhibits sufficient hardness as a finishing material for sports floors and parking lots, and can ensure sufficient pot life throughout the year. In addition, the method for constructing a urethane waterproof coating layer for sports floors and parking lots of the present invention is also excellent in practical workability and durability, and is also excellent in terms of environmental compatibility because no specialized raw materials are used.

Modes for Carrying Out the Invention

[0013] The present invention relates to a two-component, hand-applied urethane waterproofing material composition. Here, "two-component" refers to a main agent and a hardener. "Hand-applied" means that it is used by hand, applying it with a trowel, spatula, roller, brush, etc. In order to ensure sufficient performance as a waterproofing layer for sports floors and parking lots, the hardness of the cured coating film of the two-component, hand-applied urethane waterproofing material composition of the present invention is preferably in the range of 35 to 60 on the JIS D hardness scale (Durometer hardness test type D) according to the hardness test method for vulcanized rubber and thermoplastic rubber specified in JIS K 6253, and more preferably in the range of 37 to 50. If the JIS D hardness is less than 35, the anti-slip properties, aggregate retention properties, and abrasion resistance will be insufficient, and if it exceeds 60, delamination will easily occur between the general-purpose urethane layer and the two-component, hand-applied urethane waterproofing material composition.

[0014] The present invention provides a two-component, hand-applied urethane waterproofing material composition comprising a main component containing an isocyanate-terminated prepolymer composed of a polyisocyanate and a polyol, and a curing agent containing an aromatic polyamine and an inorganic filler.

[0015] (Polyisocyanate) The present invention requires the inclusion of more than 70 equivalents of isophorone diisocyanate (IPDI) as the polyisocyanate, preferably 75 equivalents or more of IPDI, and more preferably 80 equivalents or more. On the other hand, derivatives of IPDI that do not have two functionalities, such as nurates and adducts, have been commercialized, but they tend to restrict the elongation rate and therefore cannot be used in large quantities. It is preferable to use derivatives that do not have two functionalities in a range of 0 to 30 equivalents of the total polyisocyanate component.

[0016] In the present invention, polyisocyanates other than IPDI can also be used in combination. Preferred polyisocyanates that can be used in combination are mildly reactive aliphatic or alicyclic polyisocyanates, such as hexamethylene diisocyanate, norbornene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated tetramethylxylylene diisocyanate. In addition, aromatic polyisocyanates such as tolylene diisocyanate, xylylene diisocyanate, and tetramethyl xylylene diisocyanate can also be used in some cases, but tolylene diisocyanate is a specified chemical substance under the Industrial Safety and Health Act and is undesirable from an environmental standpoint.

[0017] (Main ingredient NCO content and NCO / OH equivalent ratio) This invention requires that the NCO content of the main component be between 3.0% by mass and 6.0% by mass. Within the range of plasticizer amounts in this invention, high hardness cannot be achieved unless the NCO content is 3.0% by mass or higher. On the other hand, if the NCO content exceeds 6.0% by mass, the amount of DETDA, the main component of the reactive components, also increases, resulting in a shorter pot life and problems with workability. Furthermore, in order to achieve high hardness and ensure good workability, it is preferable that the NCO content of the main component be between 3.3% by mass and 5.5% by mass. The NCO / OH equivalent ratio, which is the equivalent ratio of the NCO group of the polyisocyanate to the OH group of the polyol during the production of the main component, is preferably 1.5 to 2.5, and more preferably 1.6 to 2.3. If it is less than 1.5, the main component will thicken excessively, and if it is greater than 2.5, there will be a large amount of free polyisocyanate, which is likely to cause problems such as a decrease in elongation and a shortened pot life.

[0018] (Main ingredient: polyol) While conventionally used polyols such as polyoxyalkylene polyols, polyester polyols, and alkyl polyols can be used as the polyol component to react with the polyisocyanate, it is preferable to use polyoxyalkylene polyol as the main component, as this provides a low-viscosity prepolymer and ensures a long working time. It is preferable to include more than 50 equivalents of polyoxyalkylene polyol in the main component, and more preferably more than 70 equivalents. If the polyoxyalkylene polyol content is 50 equivalents or less, it becomes difficult to ensure low viscosity and elongation, which are desirable for workability. Furthermore, short-chain polyols such as 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, propylene glycol, and dipropylene glycol can also be used.

[0019] (Molecular weight and number of functional groups of the main polyol component) In this invention, elongation plays an important role in efficiently increasing hardness. By ensuring sufficient elongation, not only the tensile product but also the tensile strength can be efficiently increased. Conversely, attempting to increase hardness without ensuring sufficient elongation results in a material unsuitable for urethane waterproofing. Therefore, as the polyol used as the main component, it is preferable to use 10 to 97 equivalents of a diol with a molecular weight of 1500 or more in order to ensure elongation, and more preferably 20 to 80 equivalents. If 100 equivalents of a diol with a molecular weight of 1500 or more are used, the separation points in the cured product disappear and the concentration of urethane bonds decreases, which leads to a decrease in hardness development and curability, and further to a decrease in final hardness. To solve this problem, it is preferable to use a combined amount of 3 to 90 equivalents of a diol with a molecular weight of less than 1500 and a polyol with 3 or more functional groups, and more preferably 20 to 80 equivalents. It is not necessary to include both the diol with a molecular weight of less than 1500 and the polyol with 3 or more functional groups, but it is preferable to include at least one of them. It is preferable to use 0 to 90 equivalents of the diol with a molecular weight of less than 1500, and more preferably 20 to 80 equivalents. It is preferable to use 0 to 90 equivalents of the polyol with 3 or more functional groups, and more preferably 5 to 80 equivalents. By using diols with a molecular weight of less than 1500, the concentration of urethane and urea bonds in the cured product increases, allowing for high hardness without significantly compromising elongation. Furthermore, by using polyols with three or more functional groups, branching points can be created in the cured product, improving hardness development and curability, thus facilitating high hardness.

[0020] As a diol with a molecular weight of 1500 or more, a general polyoxyalkylenediol can be used, and it is preferable to use polyoxypropylenediol and polyoxyethylenepropylenediol, which have low crystallinity and low viscosity, and it is not necessary to use a special diol. As diols with a molecular weight of less than 1500, it is preferable to use polyoxyalkylenediols and short-chain polyols with molecular weights of 200 to 1200. As polyoxyalkylenediols, general polyoxypropylenediols and polyoxyethylenepropylenediols, which are low in crystallinity and viscosity, are more preferable. This allows for a high NCO content without significantly increasing the viscosity of the main component, and enables high hardness without significantly impairing the elongation. In addition, short-chain diols with molecular weights of 200 or less, such as 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, and tripropylene glycol, are preferable to use because they have high cohesive force and are effective in achieving high hardness.

[0021] Furthermore, polyether polyols with a molecular weight of 200-800, using bisphenol A as an initiator, can also be used because they have relatively high cohesive strength and are effective for increasing hardness. In addition, among polyester polyols, low-crystalline aromatic polyester polyols with a molecular weight of 300-800, such as amorphous polyols like 2-methyl-1,3-propanediol and 3-methyl-1,5-pentanediol, can be used because they have good alkali resistance and high cohesiveness.

[0022] As polyols with three or more functional groups, polyoxyalkylentriols with a molecular weight of 500 or more can be used, and general polyoxypropylene triols or polyoxyethylene propylene triols are preferred. Furthermore, polyoxypropylene polyols or polyoxyethylene propylene polyols with four or more functional groups tend to restrict elongation, so they can be used in small quantities. Polyoxyalkylentriols with a molecular weight of less than 500 can also be used, and polyoxypropylenetriols or polyoxyethylenepropylenetriols are preferred, but they tend to restrict the elongation rate, so they can only be used in small amounts. Furthermore, trifunctional polyols such as trimethylolpropane and glycerin, and polyols with four or more functions such as pentaerythritol and sorbitol, tend to restrict elongation, so they can only be used in small amounts.

[0023] (Main ingredient synthesis method) In the synthesis method for isocyanate-terminated prepolymers, the reaction is not easily promoted by simply heating polyisocyanate and polyol, so it is preferable to use a catalyst. While general urethane catalysts can be used, organostincine catalysts such as DBTDL and DOTDL are preferred, as they can efficiently promote the reaction with the addition of small amounts, 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. Furthermore, it is preferable to deactivate the catalyst with phosphoric acid or the like after the reaction is complete.

[0024] (Active hydrogen in the curing agent) As a curing agent, in order to achieve high hardness, it is necessary that more than 80 equivalents of the reactive components be aromatic polyamines, and more than 90 equivalents is preferable. Polyols as reactive components have some effect in ensuring elongation, but because they have lower cohesiveness than aromatic polyamines, they are not very effective in achieving high hardness. Furthermore, it is necessary that more than 70 equivalents of the aromatic polyamine be diethyltoluenediamine (DETDA), preferably more than 80 equivalents, and more preferably more than 90 equivalents. If the amount of amorphous and highly reactive DETDA is 70 equivalents or less, it becomes difficult to ensure good reactivity with IPDI, resulting in curability and high hardness.

[0025] As for the curing agent, aromatic polyamines that can be used in combination include Curehard MED (4,4′-methylenebis(2-ethyl-6-methylaniline)) manufactured by Kumiai Chemical Industry Co., Ltd., which has high reactivity similar to 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.; and Kayabond C-400 (4,4′-methylenebis(2,6-diiso-propylaniline)) manufactured by Nippon Kayaku Co., Ltd. Although they are less reactive aromatic polyamines, EtaCure 420 (4,4′-methylenebis(N-sec-butylaniline)) and EtaCure 300 (dimethylthiotoluenediamine) manufactured by Albemarle Co., Ltd. can also be used.

[0026] Polyols may be used as a reaction component as long as their concentration is 20 equivalents or less. Preferred polyols are those with a molecular weight of less than 1500, including short-chain polyols such as 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, ethylene glycol, diethylene glycol, dipropylene glycol, and tripropylene glycol, as well as polyester polyols and polycarbonate polyols, which are relatively highly cohesive. Among these, primary hydroxyl group polyols are more preferred because they are more reactive and less likely to remain unreacted, and among these, 1,3-propanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, and aromatic-containing polyester polyols with a molecular weight of 300 to 800 are even more preferred for achieving high hardness. Furthermore, as the aromatic polyester polyol, a liquid product using a low-crystallinity polyol, such as Kurapol (manufactured by Kuraray Co., Ltd.), is preferred. Furthermore, polyols with a molecular weight of 1500 or more can also be used, including low-viscosity polyols such as polyoxypropylene polyols and polyoxyethylene propylene polyols, but these are undesirable from the standpoint of achieving high hardness due to their low cohesiveness.

[0027] (Solvent) In the present invention, the solvent contains more than 30% by mass of an aprotic solvent having a solubility parameter (SP value) of 8.0 to 14.0, and the total solvent needs to be blended into the curing agent or both the main agent and the curing agent so as to be 10% to 40% by mass based on the urethane waterproofing material composition. Here, aprotic means that it does not contain active hydrogen (hydroxyl group, amino group, carboxylic acid group, etc.) that reacts with the isocyanate group of the isocyanate group-terminated prepolymer contained in the main agent. The solubility parameter (SP value) in the present invention refers to the Hansen solubility parameter, which is an index serving as a measure of the solubility of a binary solution. For calculating the SP value δ ((cal / cm 3 ) 1 / 2 ) of each solvent, the following formula (1) was used. δ = ((δd 2 + δp 2 + δh 2 ) / 4.2) 1 / 2 ···(1) Here, δd is the London dispersion force term, δp is the molecular polarization term, and δh is the hydrogen bond term. Also, it can be calculated based on the values (δd, δp, δh: unit (J / cm 3 )) described in the Hansen solubility parameter software (HSPiP ver.4.1.x) or “HANSEN SOLBILITY PARAMETERS” A User's Handbook Second Edition. 1 / 2 ) [[ID=Q2]]Also, when using a plurality of solvents, the SP value is obtained as the weighted average of the SP values of each solvent according to the following formula (2). m = δ1φ1 + δ2φ2 ···(2) Here, δ1 and δ2 are the SP values of each solvent component, and φ1 and φ2 are the volume fractions of each solvent component.

[0028] In the present invention, the total amount of solvent must be 10% to 40% by mass relative to the urethane waterproofing material composition, preferably 15% to 30% by mass, and is blended either as a curing agent or separately as both the main component and the curing agent. If the total amount of solvent is less than 10% by mass relative to the waterproofing material composition, it is difficult to ensure a sufficient pot life. On the other hand, if the total amount of solvent exceeds 40% by mass relative to the urethane waterproofing material composition, it is undesirable because there is a risk of shrinkage due to volatilization after application and it tends to cause inorganic fillers to settle easily. In the present invention, more than 30% by mass of the total solvent must be an aprotic solvent with a solubility parameter (SP value) of 8.0 to 14.0, preferably 35% by mass or more, and more preferably 40% by mass or more. Alternatively, the entire solvent may be an aprotic solvent with a solubility parameter (SP value) of 8.0 to 14.0. If the aprotic solvent is 30% by mass or less of the total solvent, it is difficult to ensure a sufficient pot life. If the solubility parameter (SP value) of the aprotic solvent is less than 8.0, it is difficult to ensure a sufficient pot life, and if it is greater than 14.0, the hardness of the coating film will be insufficient, which is undesirable. On the other hand, if the aprotic solvent is 70% by mass or less of the total solvent, it may be used in combination with an aprotic solvent having a solubility parameter (SP value) of less than 8.0 or greater than 14.0. Nonpolar solvents with a solubility parameter (SP value) of less than 8.0 or greater than 14.0 that can be used in combination include aromatic petroleum hydrocarbon solvents, aliphatic and alicyclic petroleum hydrocarbon solvents, and alicyclic hydrocarbon solvents having 7 to 10 carbon atoms. Specifically, MC-2000 solvent (a mixture of normal paraffins and isoparaffins having 9 to 11 carbon atoms, manufactured by Sankyo Chemical Co., Ltd.) is preferably used. In the present invention, it is preferable not to use protic solvents that may react with the isocyanate group of the isocyanate-terminated prepolymer contained in the main component.

[0029] In this invention, aprotic solvents such as ethers, esters, ketones, nitriles, and aromatic hydrocarbons with a solubility parameter (SP value) of 8.0 to 14.0 can be used. Examples of ethers or esters include dialkyl glycol ethers such as ethylene glycol dimethyl ether (SP value = 8.6), diethylene glycol dimethyl ether (SP value = 8.8), diethylene glycol diethyl ether (SP value = 8.7), and diethylene glycol dibutyl ether (SP value = 8.3); cyclic ethers such as 1,4-dioxane (SP value = 10.0); aromatic ethers such as anisole (SP value = 9.4); ethylene glycol monomethyl ether acetate (SP value = 10.0), ethylene glycol monoethyl ether acetate (SP value = 9.6), ethylene glycol monobutyl ether acetate (SP value = 8.9); and diethylene glycol monoethyl ether Examples include glycol ether acetates such as acetate (SP value = 9.4), diethylene glycol monobutyl ether acetate (SP value = 9.0), propylene glycol monomethyl ether acetate (SP value = 8.7), propylene glycol monoethyl ether acetate (SP value = 9.0), dipropylene glycol monomethyl ether acetate (SP value = 9.2), and butylene glycol monomethyl ether acetate (SP value = 8.7); carbonate esters such as dimethyl carbonate (SP value = 9.9) and diethyl carbonate (SP value = 8.8); fatty acid esters such as ethyl acetate (SP value = 9.1) and γ-butyrolactone (SP value = 12.6); and benzoic acid esters such as methyl benzoate (SP value = 10.5). Other examples include ketones such as acetylacetone (SP value = 10.6) and acetophenone (SP value = 10.6), nitriles such as acetonitrile (SP value = 11.9) and benzonitrile (SP value = 8.4), amides such as N,N-dimethylformamide (SP value = 12.1) and N,N-dimethylformacetamide (SP value = 10.8), and aromatic hydrocarbons such as toluene (SP value = 8.9) and 1,2-dichlorobenzene (SP value = 10.0). Among them, diethylene glycol dimethyl ether (SP value = 8.8), 1,4-dioxane (SP value = 10.0), anisole (SP value = 9.4), propylene glycol monomethyl ether acetate (SP value = 8.7), butylene glycol monomethyl ether acetate (SP value = 8.7), dimethyl carbonate (SP value = 9.9), diethyl carbonate (SP value = 8.8), ethyl acetate (SP value = 9.1), γ-butyrolactone (SP value = 12.6), methyl benzoate (SP value = 10.5), acetylacetone (SP value Preferably, the following are used: acetophenone (SP value = 10.6), acetonitrile (SP value = 11.9), benzonitrile (SP value = 8.4), N,N-dimethylformamide (SP value = 12.1), N,N-dimethylformacetamide (SP value = 10.8), toluene (SP value = 8.9), and 1,2-dichlorobenzene (SP value = 10.0), with propylene glycol monomethyl ether acetate (SP value = 8.7) and butylene glycol monomethyl ether acetate (SP value = 8.7) being the most preferred.

[0030] The boiling point of the solvent used in this invention is preferably in the range of 70 to 250°C, and more preferably in the range of 100 to 200°C. If the boiling point exceeds 250°C, the solvent is more likely to remain in the waterproof coating film without volatilizing, which can cause problems such as a decrease in hardness. On the other hand, if the boiling point is below 70°C, the solvent is more likely to volatilize from the curing agent, which is undesirable as it can cause problems with the stability of the curing agent and the working environment.

[0031] (Inorganic fillers) The hardening agent must contain 20% to 80% by mass of inorganic filler. Without the reinforcing effect of the inorganic filler, achieving high hardness becomes inefficient, and the waterproofing material will not be practical. If the amount of inorganic filler is less than 20% by mass, the reinforcing effect will be insufficient, and if it exceeds 80% by mass, the viscosity will increase, worsening the workability. The amount of inorganic filler to be added is preferably 30% to 75% by mass, and more preferably 40% to 70% by mass.

[0032] Calcium carbonate is preferred as an inorganic filler. Calcium carbonate is economically efficient, has good dispersibility during hardener production, exhibits little thickening even when added in large quantities, easily reduces sedimentation during hardener storage, and has minimal adverse effects on physical properties. Various types of calcium carbonate exist, including heavy calcium carbonate, light calcium carbonate, and surface-treated colloidal calcium carbonate, and any type can be used. Surface-treated colloidal calcium carbonate can be used to impart thixotropy to the material, making it suitable for use as a vertical waterproofing material. In addition, inorganic fillers such as silica, kaolin, talc, bentonite, aluminum hydroxide, and barium hydroxide can be used in part. It should be noted that these inorganic fillers contain adhering water, resulting in a water content of approximately 1000 ppm to 3000 ppm in the hardener. This adhering water is thought to gradually react with excess isocyanate groups after the two-component mixture, contributing to improved physical properties.

[0033] (Plasticizer) Next, in order to ensure a working time sufficient for construction throughout the year and to secure high elongation and high hardness, 3 to 25 parts by mass of plasticizer are required per 100 parts by mass of isocyanate group-terminated prepolymer in the main component, preferably 7 to 20 parts by mass, and most preferably 8 to 15 parts by mass. If the amount of plasticizer is less than 3 parts by mass, it becomes difficult to secure the working time and elongation, and if it exceeds 25 parts by mass, it becomes difficult to achieve high hardness. In principle, the plasticizer is blended with the curing agent, but it is also possible to blend a portion of it with the main component.

[0034] As plasticizers, plasticizers that can be commonly blended into urethane resins can be used. Examples include phthalate esters such as diisononyl phthalate (DINP), dioctyl phthalate (DOP), and butyl benzyl phthalate (BBP), aliphatic dibasic acid esters, phosphate esters, trimellitic acid esters, sebacate acid esters, epoxy fatty acid esters, glycol esters, animal and vegetable oil-based fatty acid esters, petroleum and mineral oil-based plasticizers, and alkylene oxide polymerization-based plasticizers. In particular, diisononyl phthalate (DINP) and dioctyl phthalate (DOP), which have a flash point of 200°C or higher, are preferable to use because they do not easily lose weight over the long term, are aromatic polyesters, and are resistant to hydrolysis.

[0035] (Amino group equivalent per unit of plasticizer) When the main agent and the curing agent are mixed, the ratio of the amount of amino groups (milliequivalents) of aromatic polyamine to the amount of plasticizer (g), "amino groups (milliequivalents) / plasticizer (g)" (hereinafter also referred to as "amino group equivalents per plasticizer"), must be in the range of 4.0 to 45.0, preferably 4.5 to 40.0, and most preferably 5.0 to 35.0. If the "amino group equivalents per plasticizer" is less than 4.0, the concentration of aromatic polyamine becomes low, making it difficult to achieve high hardness, and if it exceeds 45.0, it becomes difficult to ensure a sufficient pot life and elongation. To achieve high hardness while ensuring elongation, the role of polyol as a reactive component is not very important; rather, the amount of plasticizer used and the "amino group equivalents per plasticizer" play important roles.

[0036] (Isocyanate group / Aromatic amino group equivalent ratio) It is preferable to set the equivalent ratio of the isocyanate group of the main component to the amino group of the aromatic polyamine, which is a reactive component in the curing agent (hereinafter referred to as the "isocyanate group / aromatic amino group equivalent ratio") in the range of 0.9 to 1.5, more preferably 0.92 to 1.40, and even more preferably 0.95 to 1.35. If the isocyanate group / aromatic amino group equivalent ratio exceeds 1.5, it becomes difficult to achieve high hardness, and if it is less than 0.9, there will be many terminal amino groups during the curing process, resulting in poor physical properties.

[0037] (Curing accelerator) In this invention, organodin compounds, tertiary amines, metal carboxylate salts, etc., which are known to have a moisture-curing accelerating effect in reactions with isocyanate groups, can be used as reaction accelerators. Examples of organostincrine compounds include dibutyltin oxide, dioctyltin oxide, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin di-2-ethylhexanoate, dioctyltin diacetate, dioctyltin dilaurate, dibutyltin dimercaptide, dibutyltin bisacetylacetonate, dibutyltin oxylaurate, dioctyltin dineodecanate, dibutyltin bisbutylmalate, and dioctyltin 2-ethylhexylmalate, with dibutyltin dilaurate and dioctyltin dilaurate being preferred. It is preferable to use the organostincrine compound in the curing agent at a concentration of 0.001 to 0.1% by mass.

[0038] As tertiary amines, common tertiary amines such as triethylamine, tributylamine, triethylenediamine, N-ethylmorpholine, bis(2-morpholinoethyl) ether, and diazabicycloundecene can be used. However, imidazole compounds, which are special tertiary amines, are preferred in terms of foam suppression and high hardness development promotion effects. Examples of imidazole compounds that can be used include compounds having substituents at the 1st and 2nd positions, such as 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-benzyl-2-methylimidazole, and 1-benzyl-2-phenylimidazole, or compounds having a substituent at the 1st position, such as 1-methylimidazole and 1-allyliimidazole. Among these, imidazole compounds having substituents at the 1st and 2nd positions are more preferred because they have a high hardness development promotion effect. It is preferable to use 0.01 to 2.0% by mass of the tertiary amine in the curing agent.

[0039] In addition, metal carboxylates, which are generally used as urethane catalysts, can also be used. Although metal carboxylates have a weak moisture-curing acceleration effect, they strongly promote the reaction with aromatic polyamines and shorten the pot life and curing time, so they are preferable to use as a winter catalyst rather than a summer catalyst. Examples of metal carboxylates include 2-ethylhexanoic acid, neodecanoic acid, naphthenic acid, oleic acid, linoleic acid, linolenic acid, lead salts, zinc salts, bismuth salts, zirzirconium salts, tin salts, copper salts, magnesium salts, calcium salts, strontium salts, and barium salts of resin acids. Among these, calcium 2-ethylhexanoate and zinc 2-ethylhexanoate are preferred because they have a high effect in promoting the development of high hardness. It is preferable to use 0.1 to 4.0% by mass of the metal carboxylate in the curing agent. On the other hand, lead carboxylate has a high effect in shortening the pot life and curing time, but does not show much effect in promoting the development of high hardness, and its use is also undesirable from an environmental perspective.

[0040] As described above, compounds that are thought to promote moisture hardening can be used, but among them, organodin compounds and imidazole compounds can both promote high hardness without shortening the pot life and also have excellent foam suppression properties, and can be used particularly as catalysts in summer. Furthermore, imidazole compounds are preferable because, unlike metal catalysts which tend to accelerate thermal degradation when added in large quantities, they hardly accelerate thermal degradation even when added in large amounts. While moisture-curing accelerators are generally incorporated into the curing agent, a considerable amount can be added at the construction site during the two-component mixing process. On the other hand, while it is possible to incorporate them into the main component, this is not highly preferable as it may impair storage stability.

[0041] On the other hand, carboxylic acids or acid anhydrides are effective in shortening the pot life and curing time because they promote the reaction between the IPDI prepolymer and aromatic polyamine, and they hardly promote thermal degradation like carboxylic acid metal salts, so they can be preferably used as accelerators, especially for winter use. However, since they have almost no moisture curing effect, the effect of promoting high hardness development cannot be expected to be very high in formulations with a high isocyanate group / aromatic amino group equivalent ratio. Examples of carboxylic acids include propionic acid, 2-methylpentanoic acid, octic acid, isononanoic acid, and naphthenic acid, with octic acid being preferred among them. Examples of acid anhydrides include phthalic anhydride, hexahydrophthalic anhydride, methyl-hexahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, succinic anhydride, and maleic anhydride, with methyl-tetrahydrophthalic anhydride being preferred. It is desirable to use 0.05 to 2.0% by mass of carboxylic acids and acid anhydrides in the curing agent, and some or all of them may be incorporated into the main component.

[0042] Furthermore, it is preferable to either pre-mix the acid anhydride catalyst into the main component or to mix the acid anhydride when mixing the main component and the hardener. However, adding the acid anhydride at the construction site each time construction is performed presents problems such as storage and management issues with the acid anhydride, and measurement errors due to the complexity at the construction site. Therefore, it is more preferable to pre-mix the acid anhydride into the main component.

[0043] (Other additives) In addition, the curing agent may contain additives such as wetting agents, defoaming agents, pigments, and weather-resistant agents as needed.

[0044] (Main component / Hardener mixing ratio) The mixing ratio of the main component to the hardener is not particularly limited, but it is preferably in the range of 1 / 1 to 1 / 2 by mass ratio. However, generally, when the ratio is 1 / 2, the amount of plasticizer increases, which is unfavorable for achieving high hardness, so it is preferable that it be 1 / 1 to 1 / 1.75, and more preferably 1 / 1 to 1 / 1.5.

[0045] (Waterproofing method for sports floors and parking lots) The present invention relates to a method for applying urethane waterproof coatings for sports floors and parking lots. The application method of the present invention cannot be used to directly apply the material to inorganic substrates such as concrete. In the case of inorganic substrates, the urethane waterproofing material will not adhere to them, so it is possible to apply the material after applying a primer that can block some of the moisture in the substrate and ensure adhesion. In addition, during renovations, it may be possible to apply the material on top of the existing urethane waterproofing layer by applying an intermediate primer. Furthermore, the material can be applied to inorganic substrates after fixing a breathable buffer sheet, a polymer sheet such as a PVC sheet, a rubber sheet, or a nonwoven fabric sheet with a primer, adhesive, mechanical fixing, or loose laying. Moreover, even in the case of metal substrates, adhesion cannot be ensured by directly applying the application method of the present invention for sports floors or parking lot urethane waterproofing coatings, so it is possible to apply the material after applying a dedicated primer.

[0046] The present invention provides a urethane waterproof coating layer for sports floors and parking lots that offers excellent practical workability and durability, and is environmentally friendly as it does not use any raw materials subject to the Specified Chemical Substances Act. This is achieved by applying a primer layer to a substrate surface, or by applying a primer layer and a general-purpose urethane waterproofing material layer, followed by mixing the two-component, hand-applied urethane waterproofing material composition of the first invention with inorganic aggregate and applying the mixture.

[0047] The primer layer of the present invention can be one that is normally used for urethane waterproofing layers, but generally a water-based primer is used. The water-based primer is not particularly limited, and emulsion-type water-based primers such as epoxy resin-based, urethane resin-based, vinyl acetate resin-based, acrylic resin-based, styrene-butadiene rubber-based, and chloroprene rubber-based primers can be used. Preferably, epoxy resin systems include those comprising two components: a main component consisting of an emulsion mainly composed of bisphenol A type, novolac type, brominated type, alicyclic type, or aliphatic type epoxy resin, and a curing agent consisting of an emulsion containing aliphatic polyamines, aromatic polyamines, alicyclic polyamines, polyamides, etc. Furthermore, the urethane resin system consists of a main component, which is an emulsion mainly composed of polyol, and a curing agent, which is a liquid MDI such as crude MDI or a modified carbodiimide. In particular, a preferred primer is a one-component moisture-curing polyurethane resin. These primers may also contain fillers such as Portland cement to fill pinholes in the substrate. These primer materials are applied to the substrate using painting tools such as brushes, rollers, or rakes, but the amount used and the thickness of the coating are not particularly limited, as long as it is enough to reliably bond the substrate and the polyurethane layer. Typically, the amount of primer layer applied is 0.15 to 0.20 kg / m². 2 Preferably, about 0.20 kg / m 2 That is the case.

[0048] In the construction method of the present invention, the general-purpose urethane waterproofing material used in the urethane waterproofing layer is not particularly limited, and any commercially available general-purpose urethane waterproofing material can be used. As a general-purpose urethane waterproofing material, one specified as a high-elongation type according to JIS A 6021 "Waterproofing coating material for buildings" is preferred, and among these, one with relatively high strength and high hardness is preferred.

[0049] In the construction method of the present invention, the hardness of the hardened film of the high-hardness two-component hand-applied urethane waterproofing material composition used must be in the range of 35 to 60 on the JIS D hardness scale (Durometer hardness test type D) according to the hardness test method for vulcanized rubber and thermoplastic rubber specified in JIS K 6253, and more preferably between 35 and 50. If the JIS D hardness is less than 35, the slip resistance, aggregate retention, and abrasion resistance will be insufficient, and if it exceeds 60, delamination will easily occur between the general-purpose urethane layer and the two-component hand-applied urethane waterproofing material composition. Furthermore, in this construction method, the tensile strength of the hardened film of the hardened film of the two-component hand-applied urethane waterproofing material composition used must be 10 N / mm². 2 Preferably, the above, the elongation rate is preferably 300% or more, and the tensile product is preferably 700 N / mm or more. Tensile strength is 10 N / mm 2 Below these limits, slip resistance, aggregate retention, and abrasion resistance become insufficient. If the elongation rate is less than 300%, delamination is likely to occur between the general-purpose urethane layer and the two-component hand-applied urethane waterproofing material composition. If the tensile strength is less than 700 N / mm, crack-following ability decreases, and problems such as peeling and blistering from the substrate become more likely. This invention is not intended for the repair of asphalt-based waterproofing layers, but rather for the waterproofing and protection of inorganic substrates such as concrete, metal substrates, polymer resin substrates, and rubber substrates. Furthermore, when using the two-component, hand-applied urethane waterproofing material composition of this invention in areas exposed to direct sunlight, it is generally recommended to apply a topcoat.

[0050] In the application method of the present invention, examples of inorganic aggregates to be mixed with the high-hardness two-component hand-applied urethane waterproofing material composition include silica sand, crushed porcelain aggregate, ceramic aggregate, ferroalloy lag, and hollow balloons. These aggregates are uniformly scattered immediately after or simultaneously with the application of the high-hardness two-component hand-applied urethane waterproofing material composition, and it is preferable that the particle size is 0.05 to 5.0 mm, and more preferably 0.1 to 3.0 mm. The inorganic aggregate is added to the high-hardness two-component hand-applied urethane waterproofing material composition at a rate of 0.3 to 1.5 kg / m³. 2 Preferably, it should be included in a quantity of 0.3 to 1.0 kg / m². 2It is preferable that it be included. As inorganic aggregates, for example, Inseragate® 1005 and 2010 (manufactured by Nissei Sangyo Co., Ltd.), Powercron G (Fukushima sand, manufactured by Toto Kosan Co., Ltd.), AD aggregate (manufactured by AGC Polymer Building Materials Co., Ltd.), Sakurabashi S sand No. 4 and No. 5 (manufactured by Cosmo Energy Solutions Co., Ltd.), silica sand No. 4 and No. 5 (manufactured by Tohoku Silica Sand Co., Ltd.) are preferably used. [Examples]

[0051] raw materials The raw materials used in the following examples and comparative examples are as follows: [Isocyanate] IPDI: Isophorone diisocyanate, VESTANAT® IPDI (trade name), NCO content 37.8% by mass, NCO functional group count approximately 2.0, manufactured by Evonik Japan Co., Ltd. [Polyol] PA-2000: Polyoxypropylene diol, Sannix® PA-2000, average molecular weight 2000 (product name), OH value 56.1 mg KOH / g, manufactured by Sanyo Chemical Industries, Ltd. GA-3000: Sannix (registered trademark) GA-3000 (product name), polyoxypropylene triol, average molecular weight 3000, OH value: 56.1 mg KOH / g, manufactured by Sanyo Chemical Industries, Ltd. GP-600: Polyoxypropylene triol, Sannix® GP-600 (product name), average molecular weight 600, OH value: 279 mg KOH / g, manufactured by Sanyo Chemical Industries, Ltd. P-2010: Aliphatic polyester diol, Kuraray polyol P-2010, average molecular weight 2000, OH value: 56.1 mg KOH / g, manufactured by Kuraray Co., Ltd. P-510: Aliphatic polyester diol, Kuraray polyol P-510, average molecular weight 500, OH value: 224.4 mg KOH / g, manufactured by Kuraray Co., Ltd. F-1010: Aliphatic polyester triol, Kuraray polyol F-1010, average molecular weight 10000, OH value: 167.4 mg KOH / g, manufactured by Kuraray Co., Ltd. BP-5P: Polyoxypropylene diol, Newpol® BP-5P, average molecular weight 500, OH value: 209 mg KOH / g, manufactured by Sanyo Chemical Industries, Ltd. 1,4-BD:1,4-Butanediol (trade name), manufactured by Mitsubishi Chemical Corporation. [Polyamines] DETDA: Diethyltoluenediamine, Etacure 100 (product name), manufactured by Albemarle Japan Co., Ltd. 〔catalyst〕 DOTDL: Dioctyl tin dilaurate, KS-1200A-1 (product name), manufactured by Kyodo Yakuhin Co., Ltd. NC-IM: 1-Isobutyl-2-methylimidazole, DABCO® registered trademark NC-IM (trade name), manufactured by Air Products Japan Co., Ltd. 〔solvent〕 MC-2000: MC-2000 Solvent (product name), a mixture of normal paraffins and isoparaffins with 9 to 11 carbon atoms, manufactured by Sankyo Chemical Co., Ltd. PMA: Propylene glycol monomethyl ether acetate, PMA (trade name), manufactured by Sankyo Chemical Co., Ltd. DMSO: Tetrahydrothiophene-1,1-dioxide, manufactured by Tokyo Chemical Industry Co., Ltd. PGME: Propylene glycol monomethyl ether, manufactured by Tokyo Chemical Industry Co., Ltd. DMC: Dimethyl carbonate, manufactured by Tokyo Chemical Industry Co., Ltd. Digrime: Diethylene glycol dimethyl ether, manufactured by Tokyo Chemical Industry Co., Ltd. Dioxane: 1,4-dioxane, manufactured by Tokyo Chemical Industry Co., Ltd. Acetylacetone: Acetylacetone, manufactured by Tokyo Chemical Industry Co., Ltd. Acetonitrile: Acetonitrile, manufactured by Tokyo Chemical Industry Co., Ltd. DMF: N,N-dimethylformamide, manufactured by Tokyo Chemical Industry Co., Ltd. DMAC: N,N-dimethylacetamide, manufactured by Tokyo Chemical Industry Co., Ltd. Toluene: Toluene, manufactured by Tokyo Chemical Industry Co., Ltd. Metoacetate: Methoxybutyl acetate, manufactured by Sankyo Chemical Co., Ltd. DEC: Diethyl carbonate, manufactured by Tokyo Chemical Industry Co., Ltd. Ethyl acetate: Ethyl acetate, manufactured by Tokyo Chemical Industry Co., Ltd. Anisole: Anisole, manufactured by Tokyo Chemical Industry Co., Ltd. O-DCB: 1,2-dichlorobenzene, manufactured by Tokyo Chemical Industry Co., Ltd. Benzonitrile: Benzonitrile, manufactured by Tokyo Chemical Industry Co., Ltd. Methyl benzoate: Methyl benzoate, manufactured by Tokyo Chemical Industry Co., Ltd. Acetophenone: Acetophenone, manufactured by Tokyo Chemical Industry Co., Ltd. γ-Butyrolactone: γ-Butyrolactone, manufactured by Tokyo Chemical Industry Co., Ltd. [Plasticizer] DINP: Diisononyl phthalate, Sansoizer® DINP (product name), manufactured by Shin Nippon Rika Co., Ltd. [Inorganic fillers] NS#100: Calcium carbonate, NS#100 (product name), manufactured by Nitto Funka Kogyo Co., Ltd. Additives: Manufactured by Kusumoto Kasei Co., Ltd. [Commercially available waterproofing material auxiliary materials] Fast-curing OT Primer M Blue, OT Primer QQ, OT Coat QQ (manufactured by Tajima Roofing Co., Ltd.) [Inorganic aggregate] Inseragate (registered trademark) 1005 (manufactured by Nissei Sangyo Co., Ltd.)

[0052] Preparation of the main ingredient According to the formulations in Tables 1 to 9, the specified polyol, solvent, and dioctyl tin dilaurate were charged into a four-necked flask, followed by the specified polyisocyanate compound. The mixture was then reacted at 90-100°C for 1-2 hours with stirring to obtain each main component.

[0053] Preparation of hardening agent According to the formulations in Tables 1 to 9, the specified liquids were placed in a metal container, mixed at low speed with a stirrer (dissolver blade) until homogenized, then a predetermined amount of calcium carbonate was added and mixed at 1500 rpm for 10 minutes to obtain each hardening agent.

[0054] Example 1 In Example 1, the main component and hardener were obtained according to the formulation shown in Table 1. These main component and hardener were mixed in a mass ratio of 1:1 to obtain a urethane waterproofing material composition. In Example 1, MC-2000, with a solubility parameter (SP value) of 7.2 to 7.8, was used as the solvent at a concentration of 20% by mass relative to the main component, and PMA, with a solubility parameter (SP value) of 8.7, was used at a concentration of 15% by mass relative to the hardener. The pot life of Example 1 was 40 minutes, and the JIS D hardness of the cured coating film was 41. This demonstrated good coating film properties as a finishing material for two-component, hand-applied urethane waterproofing layers for sports floors and parking lots, while also ensuring a sufficient pot life for winter use.

[0055] Comparative Example 1 Comparative Example 1 was conducted in the same manner as Example 1, except that MC-2000, which has a solubility parameter (SP value) of 7.2 to 7.8, was used as the solvent for the curing agent instead of PMA. The pot life of Comparative Example 1, which did not use an aprotic solvent with a solubility parameter (SP value) of 8.0 to 14.0, was 28 minutes, which was shorter than that of Example 1. The JIS D hardness of the cured coating film was 41, and it showed good coating film properties as a two-component, hand-applied urethane waterproofing layer for sports floors and parking lots, but the pot life was insufficient even as a winter formulation.

[0056] Comparative Example 2 Comparative Example 2 was carried out in the same manner as Example 1, except that DMSO with a solubility parameter (SP value) of 14.5 was used as the solvent for the curing agent instead of PMA. The pot life of Comparative Example 2 was 84 minutes, and the JIS D hardness of the cured coating film was 25. The pot life was sufficient even for a summer formulation, but the coating film properties such as hardness were insufficient for a two-component, hand-applied urethane waterproofing layer for sports floors and parking lots.

[0057] Example 2 Example 2 was carried out in the same manner as Example 1, except that the NCO / OH equivalent ratio of the main component was adjusted to an NCO content of 3.64% by mass, and the amount of plasticizer used was 10.69 parts by mass per 100 parts by mass of prepolymer. The pot life of Example 2 was 66 minutes, and the JIS D hardness of the cured coating film was 35. It showed good coating film properties as a two-component, hand-applied urethane waterproofing layer for sports floors and parking lots, and also ensured a sufficient pot life for summer use.

[0058] Example 3 Example 3 was carried out in the same manner as Example 2, except that meteorite with a solubility parameter (SP value) of 8.7 was used as the solvent for the curing agent instead of PMA. The pot life of Example 3 was 62 minutes, and the JIS D hardness of the cured coating film was 35. It showed good coating film properties as a two-component, hand-applied urethane waterproofing layer for sports floors and parking lots, and also ensured a sufficient pot life for summer use.

[0059] Comparative Example 3 Comparative Example 3 was carried out in the same manner as Example 2, except that MC-2000 was used instead of PMA as the solvent for the curing agent. Comparative Example 3, which did not use an aprotic solvent with a solubility parameter (SP value) of 8.0 to 14.0, had a pot life of 43 minutes, which was shorter than that of Example 2. The JIS D hardness of the cured coating film was 35, and it showed good coating film properties as a two-component, hand-applied urethane waterproofing layer for sports floors and parking lots, but the pot life was insufficient for a summer formulation.

[0060] Comparative Example 4 Comparative Example 4 was carried out in the same manner as Example 2, except that PGME, a protic solvent with a solubility parameter (SP value) of 11.3, was used as the solvent for the curing agent instead of PMA, an aprotic solvent. The pot life of Comparative Example 4, which used PGME, a protic solvent with a solubility parameter (SP value) in the range of 8.0 to 14.0 that may react with the isocyanate group in the main component, was 21 minutes, which was shorter than that of Example 2. The JIS D hardness of the cured coating film was 35, and it showed good coating film properties as a two-component, hand-applied urethane waterproofing layer for sports floors and parking lots, but the pot life was insufficient even as a winter formulation.

[0061] Examples 4-7 Examples 4-7 were conducted in the same manner as Example 1, except that instead of PMA, DMC with a solubility parameter (SP value) of 9.9, diglyme with a solubility parameter of 8.8, dioxane with a solubility parameter of 10.0, and acetylacetone with a solubility parameter of 10.6 were used as solvents for the curing agent. The pot life of Examples 4-7 was 35 minutes, 41 minutes, 35 minutes, and 40 minutes, respectively, and the JIS D hardness of the cured coating film was 41 in all cases. These examples showed good coating film properties as a two-component, hand-applied urethane waterproofing layer for sports floors and parking lots, and ensured a sufficient pot life for winter use.

[0062] Examples 8-10 Examples 8-10 were conducted in the same manner as Example 1, except that acetonitrile with a solubility parameter (SP value) of 11.9, DMF with 12.1, and DMAC with 10.8 were used as solvents instead of PMA as the curing agent. The pot life of Examples 8-10 was 64 minutes, 80 minutes, and 98 minutes, respectively, and the JIS D hardness of the cured coating film was 37 in all cases. These examples showed good coating film properties as a two-component, hand-applied urethane waterproofing layer for sports floors and parking lots, and also ensured a sufficient pot life for summer use.

[0063] Example 11 Example 11 was carried out in the same manner as Example 1, except that the NCO / OH equivalent ratio of the main component was adjusted to an NCO content of 4.00% by mass, the amount of plasticizer used was 10.98 parts by mass per 100 parts by mass of prepolymer, and the isocyanate group / aromatic amino group equivalent ratio was 1.30. The pot life of Example 11 was 57 minutes, and the JIS D hardness of the cured coating film was 41. It showed good coating film properties as a two-component, hand-applied urethane waterproofing layer for sports floors and parking lots, and also ensured a sufficient pot life for summer use.

[0064] Example 12 Example 12 was carried out in the same manner as Example 11, except that PMA with a solubility parameter (SP value) of 8.7 was used as the solvent for the main component instead of MC-2000. The pot life of Example 12 was 93 minutes, and the JIS D hardness of the cured coating film was 43. It showed good coating film properties as a two-component, hand-applied urethane waterproofing layer for sports floors and parking lots, and also ensured a sufficient pot life for summer use.

[0065] Example 13 Example 13 was carried out in the same manner as Example 12, except that the isocyanate group / aromatic amino group equivalent ratio was set to 1.15. The pot life of Example 13 was 78 minutes, and the JIS D hardness of the cured coating film was 45. It showed good coating film properties as a two-component, hand-applied urethane waterproofing layer for sports floors and parking lots, and ensured a sufficient pot life for a summer formulation.

[0066] Example 14 Example 14 was carried out in the same manner as Example 12, except that the main agent / hardener mixing ratio was 1:1.5. The pot life of Example 14 was 113 minutes, and the JIS D hardness of the cured coating film was 41. It showed good coating film properties as a two-component, hand-applied urethane waterproofing layer for sports floors and parking lots, and ensured a sufficient pot life for summer use.

[0067] Example 15 Example 15 was carried out in the same manner as Example 13, except that the amount of PMA used as the curing agent was changed to 20.08% by mass, and the amount of plasticizer used was changed to 3.75 parts by mass per 100 parts by mass of prepolymer. The pot life of Example 15 was 73 minutes, and the JIS D hardness of the cured coating film was 48. It showed good coating film properties as a two-component, hand-applied urethane waterproofing layer for sports floors and parking lots, and also ensured a sufficient pot life for summer use.

[0068] Examples 16-18 Examples 16-18 were carried out in the same manner as Example 15, except that the NCO / OH equivalent ratio of the main component was adjusted to change the NCO content to 4.55% by mass, 5.04% by mass, and 5.55% by mass, respectively. The pot life of Examples 16-18 was 62 minutes, 47 minutes, and 35 minutes, respectively, and the JIS D hardness of the cured coating film was 50, 52, and 54. These demonstrated good coating film properties as a two-component, hand-applied urethane waterproofing layer for sports floors and parking lots, and provided sufficient pot life for Example 16 (summer formulation) and Examples 17 and 18 (winter formulation).

[0069] Example 19 Example 19 was carried out in the same manner as Example 12, except that the polyol component of the main agent was polyester polyols instead of polyoxyalkylene polyols, and the amount of plasticizer used was 11.15 parts by mass per 100 parts by mass of prepolymer. The pot life of Example 19 was 72 minutes, and the JIS D hardness of the cured coating film was 38. It showed good coating film properties as a two-component, hand-applied urethane waterproofing layer for sports floors and parking lots, and also ensured a sufficient pot life for summer use.

[0070] Example 20 Example 20 was carried out in the same manner as Example 15, except that BP-5P was used instead of 1,4-BD as the main component diol with a molecular weight of less than 1500. The pot life of Example 20 was 75 minutes, and the JIS D hardness of the cured coating film was 42. It showed good coating film properties as a two-component, hand-applied urethane waterproofing layer for sports floors and parking lots, and also ensured a sufficient pot life for summer use.

[0071] Examples 21-28 Examples 21-28 were carried out in the same manner as Example 1, except that instead of PMA, the solvents used as curing agents were DEC (solubility parameter (SP value) 8.8), ethyl acetate (9.1), toluene (8.9), anisole (9.4), O-DCB (10.0), benzonitrile (8.4), methyl benzoate (10.5), and acetophenone (10.6), all with solubility parameters (SP values). The pot times for Examples 21-28 were 37 minutes, 39 minutes, 33 minutes, 34 minutes, 30 minutes, 43 minutes, 35 minutes, and 40 minutes, respectively, ensuring sufficient pot times for winter formulations.

[0072] Example 29 (Example of a multi-layered structure for a parking lot) Apply 0.15 kg / m² of "Fast-Curing OT Primer M Blue" as a penetrating primer to the surface of the concrete parking lot floor base. 2 As a film-thickening primer, use "OT Primer QQ / Cement = 3 / 2~4 / 1" at a rate of 0.15 kg / m 2 The surface was evenly coated with a roller and then allowed to dry. Next, the waterproofing layer is a hardened coating with a hardness of 32D and a tensile strength of 13.3 N / mm². 2 A high-strength, high-elongation waterproofing material conforming to JIS standards, with an elongation rate of 492% at break, is applied at a rate of 2.0 kg / m². 2 The mixture was applied using a trowel and dried, and then another layer was applied and dried in the same manner under the same conditions. Next, as a finishing material, 0.3 kg / m² of the high-hardness two-component hand-applied urethane waterproofing material composition described in Example 13 was applied. 2 Apply with a roller to achieve the desired finish, and simultaneously or immediately after application, apply Inseragate® 1005 at a rate of 0.6 kg / m². 2 The material was sprayed in this manner. After curing, the high-hardness two-component urethane waterproofing material composition for hand application described in Example 13 was further applied at a rate of 0.5 kg / m². 2 The mixture was applied and dried using a roller. Next, OT Coat QQ was applied as a top coat at a rate of 0.2 kg / m². 2 The coating was applied twice with a roller and then dried. The finished floor surface was a rough surface with a nice uneven texture. <Impact Resistance Test> The impact resistance test conducted according to the performance evaluation test method for membrane waterproofing (JASS8) showed that at 0°C and 20°C, the impact resistance was classified as 4 (no holes were made in any of the three units by an impact from a height of 1.5m), and at 60°C, it was classified as 3 (at least one unit was punctured by an impact from a height of 1.5m). <Durability Test> Abrasion resistance and aggregate delamination resistance were evaluated using a rotary labeling tester. A swivel-type caster (thermoplastic polyurethane wheel, hardness D 46) was used, with a load of 16.2 kg per wheel, a wheel travel speed of 0.9 m / sec, and a turntable rotation speed of 59.4 revolutions / minute. The degree of aggregate detachment from the test specimen was examined at 20,000 rotations. As a result, almost no aggregate detachment was observed.

[0073] The measurement methods for each evaluation item in Tables 1 to 9 are as follows.

[0074] [NCO (mass%)] Accurately weigh approximately 1 g of the main component into a 200 mL Erlenmeyer flask. Add 10 mL of 0.5 N di-n-butylamine (toluene solution), 10 mL of toluene, and an appropriate amount of bromophenol blue, then add approximately 100 mL of methanol and dissolve. Titrate this mixture with 0.25 N hydrochloric acid solution. The NCO (mass%) is determined by the following formula. NCO (mass%) = (blank titration value - 0.5N hydrochloric acid solution titration value) × 4.20² × factor of 0.25N hydrochloric acid solution × 0.25 ÷ sample weight

[0075] [Pot life (minutes)] In an air-circulating environmental test chamber with a temperature of 23°C and a humidity of 50%, the time from the start of stirring and mixing of the main agent and hardener in a predetermined ratio until the viscosity at 2 rpm reached 60,000 mPa·s was measured using a BH-type viscometer.

[0076] [Available construction time (hours)] In an air-circulating environmental test chamber with a temperature of 23°C and humidity of 50%, the waterproofing material, prepared by stirring and mixing the main agent and hardener in a predetermined ratio, was measured at a rate of 2 kg / m². 2 The time it took for the material to be applied and allowed to be walked on in shoes, even though it was not yet fully cured, and for the next step of the process to begin was measured.

[0077] [Preparation of coatings for initial physical property measurements] Based on JIS A 6021, a waterproofing material prepared by stirring and mixing the main agent and hardener in a predetermined ratio was tested at a temperature of 23°C and humidity of 50% in an air-circulating environmental test chamber at 2 kg / m². 2 The coating was applied, cured for 96 hours at a temperature of 23±2°C and a relative humidity of (50±10)%, then demolded, the coating film was turned over, and cured again for 240 hours at a temperature of 23±2°C and a relative humidity of (50±10)% to create a coating film for initial physical property measurement.

[0078] [Tensile strength (N / mm²)] 2 )] Measurements were performed using a coating film intended for initial physical property measurement, in accordance with JIS A 6021.

[0079] [Elongation at break (%)] Measurements were performed using a coating film intended for initial physical property measurement, in accordance with JIS A 6021.

[0080] [Tensile product (N / mm)] Using the tensile strength and elongation at fracture mentioned above, calculations were performed in accordance with JIS A 6021.

[0081] [JIS D Hardness (Type D Durometer)] Measurements were performed using a coating film intended for initial physical property measurement, in accordance with JIS K 6253.

[0082] [Table 1]

[0083] [Table 2]

[0084] [Table 3]

[0085] [Table 4]

[0086] [Table 5]

[0087] [Table 6]

[0088] [Table 7]

[0089] [Table 8]

[0090] [Table 9] [Industrial applicability]

[0091] The composition and application method of the present invention can be suitably used as a two-component, hand-applied urethane waterproofing material for sports floors, parking lots, and the like.

Claims

1. A two-component urethane waterproofing material composition for hand application, comprising a main component containing an isocyanate-terminated prepolymer consisting of a polyisocyanate and a polyol, and a curing agent containing an aromatic polyamine and an inorganic filler, In the main component, more than 70 equivalents of the polyisocyanates constituting the isocyanate-terminated prepolymer (where equivalent percentage is based on the number of moles of isocyanate groups) are isophorone diisocyanates, and the NCO content of the main component is 3.0% to 6.0% by mass. The curing agent contains 20% to 80% by mass of inorganic filler, and more than 80 equivalents of the total reactive components in the curing agent (however, the equivalent percentage here is based on the number of moles of active hydrogen groups). ) is an aromatic polyamine, and more than 70 equivalents of the aromatic polyamine (however, the equivalent percentage here is based on the number of moles of amino groups). ) is diethyltoluenediamine, A plasticizer is added in an amount of 3 to 25 parts by mass per 100 parts by mass of isocyanate-terminated prepolymer in the main component, either separately in the curing agent or in both the main component and the curing agent. The urethane waterproofing material composition contains 10% to 40% by mass of solvent, either in the curing agent or separately in both the main component and the curing agent, and the solvent contains more than 30% by mass of aprotic solvent with a solubility parameter (SP value) of 8.0 to 14.

0. A two-component, hand-applied urethane waterproofing material composition in which the ratio of the amount of amino groups (milli-equivalent) of aromatic polyamine to the amount (g) of plasticizer is 4.0 to 45.

0.

2. The two-component, hand-applied urethane waterproofing material composition according to claim 1, wherein the polyol constituting the isocyanate-terminated prepolymer in the main component contains a polyoxyalkylene polyol, and the polyol constituting the isocyanate-terminated prepolymer in the main component contains 10 to 97 equivalents of a diol with a molecular weight of 1500 or more (wherein equivalent percentage is based on the number of moles of hydroxyl groups) and 3 to 90 equivalents of a diol with a molecular weight of less than 1500 and a polyol with 3 or more functional groups (wherein equivalent percentage is based on the number of moles of hydroxyl groups).

3. The two-component urethane waterproofing material composition for hand application according to Claim 1, wherein the equivalent ratio of the isocyanate group of the main component to the amino group of the aromatic polyamine, which is a reactive component in the curing agent, is 0.9 to 1.

5.

4. More than 50 equivalents of the polyol constituting the isocyanate group-terminated prepolymer in the main component (however, the equivalent percentage here is based on the number of moles of hydroxyl groups). The two-component, hand-applied urethane waterproofing material composition according to claim 1, wherein ) is a polyoxyalkylene polyol.

5. The two-component, hand-applied urethane waterproofing material composition according to claim 1, wherein the hardened coating film of the urethane waterproofing material composition has a JIS D hardness of 35 to 60.

6. A method for applying a urethane waterproof coating layer, comprising applying a primer layer to a substrate surface, or applying a primer layer and a urethane waterproofing material layer, then mixing the two-component hand-applied urethane waterproofing material composition described in claim 1 with an inorganic aggregate and applying the mixture.

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