JP2018070849A - Urethane waterproof material composition and urethane waterproof method for two-liquid type environmental response hand coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an urethane waterproof material composition for two-liquid type environmental response hand coating excellent in workability through year, environmentally friendly, excellent in durability and corresponding to an urethane rubber-based high elongation shape of JIS A 6021 (coated film waterproof material for building).SOLUTION: An urethane waterproof material composition consists of a main agent containing an isocyanate group terminal prepolymer consisting of polyisocyanate and polyol, and a curing agent aromatic polyamine, a plasticizer and an inorganic filler, the polyisocyanate contains isophorone diisocyanate, the polyol contains polyoxyalkylene polyol, NCO content of the isocyanate group terminal prepolymer is over 1.2 mass% and 4.5 mass% or less, over 70 equivalent % of the curing agent in all active hydrogen is an aromatic polyamine, the aromatic polyamine contains diethyl toluenediamine, and a ratio between amino group amount of the aromatic polyamine (milliequivalent) and amount of the plasticizer (g) is 0.6 to less than 1.6.SELECTED DRAWING: None

Description

  The present invention relates to a two-component, environmentally-friendly hand-applied urethane waterproof material composition that can sufficiently ensure pot life throughout the year, and a urethane waterproofing method using the composition.

Urethane waterproofing material is suitable for construction of irregular shapes and narrow parts, so it is suitable for construction of new buildings or renovations, verandas, balconies of apartment buildings such as apartments, balconies, open corridors and flat areas on roofs of relatively large areas, It is used for elevations, parapets, and pedestals. Roughly classified, there are two types, one for fluidized flats to be applied to flatters and rooftop flats, and the other for non-fluid rises to be applied to elevations, parapets, and pedestals.
Also, a close contact method in which a urethane waterproof material is directly applied to an inorganic base such as concrete via a primer, and a vent cushion method in which a urethane waterproof material is applied on a relatively large area rooftop, etc. There is.

The two-component urethane waterproof material for hand-painting that is currently widely used is based on an isocyanate group-terminated prepolymer consisting of tolylene diisocyanate (hereinafter referred to as TDI) and polyoxypropylene polyol, and one curing agent. As the active hydrogen in the mixture, 3,3′-dichloro-4,4′-diaminodiphenylmethane (hereinafter referred to as MOCA), which is a relatively low-reactivity aromatic polyamine, is used as a main component, and low-reactivity 2 A polyoxypropylene polyol, which is a high-grade polyol, is used in combination. In order to accelerate the reaction of the low-reactivity polyoxypropylene polyol, lead carboxylate is generally used as an accelerator. When lead carboxylate is not used, the reaction with the polyol is not accelerated, and particularly in the summer, the reaction between the isocyanate group of the main agent and moisture proceeds. As a result, the carbon dioxide gas by-produces the foaming phenomenon. Raises and lowers physical properties.
The above waterproofing material is referred to as MOCA cross-linked waterproofing material, and MOCA is a raw material with high crystallinity and poor solubility, but it can be dissolved and stabilized to some extent in polyoxypropylene polyol, and it is hand-painted. Since it is a waterproof material having a pot life suitable for construction, it is still used as a general-purpose waterproof material.

A typical urethane waterproof material is a two-part liquid material mixed with a stirrer and then hand-painted with a trowel, spatula, roller, brush, etc. After mixing with a stirrer, it can be used for at least about 30 minutes (Hereinafter referred to as pot life). The pot life is generally the time from the mixing of two liquids at 23 ° C. until the viscosity reaches 60,000 mPa · s.
The two-component urethane waterproofing material for hand-painting has a summer composition suitable for construction at around 30 ° C in summer and construction at around 5 ° C in winter because the outdoor temperature differs greatly between winter construction and summer construction. In general, a waterproofing material for flats is devised so that the pot life is 30 minutes or more at the construction temperature in each season. The longer the pot life in the coating operation, the better. However, in general, the longer the pot life, the worse the curability, and the time it takes for the worker to get on the coating film to perform the next process (below) , Also called construction possible time). In a normal operation, it is desired that the urethane waterproof material is applied in the evening and the next morning is ready for construction, and the construction possible time is preferably adjusted within about 17 hours throughout the year. On the other hand, it is said that it is better to secure a longer pot life since the waterproofing material for start-up construction is more complicated than the waterproofing material for flat ground, but it is not a part to walk after construction, so the workable time is flat. It may be later than the waterproofing material, and there is no problem even if it is around 24 hours.

In addition, the MOCA cross-linked waterproof material has a large environmental problem. MOCA used for hardeners is designated as Class 2 specified chemical substances by the Occupational Safety and Health Act and is used for hardeners in excess of the upper limit of 1%. Preventive rules (hereinafter referred to as specialization rules) become applicable products. Moreover, MOCA is classified into group 1 (indicating carcinogenicity to humans) by carcinogenicity evaluation by IARC (International Cancer Research Institute).
In addition, TDI used in the main agent is also designated as a specified chemical substance, and in the main agent of general-purpose products, the free TDI exceeds 1% of the upper limit value, so the main agent is also subject to specialization rules. Therefore, various restrictions are imposed upon manufacturing and construction. Furthermore, lead carboxylate compounds used as promoters are materials that are strictly restricted worldwide, and are designated as specified Class 1 designated chemical substances in the Chemical Substances Emissions Control Management Promotion Act (commonly known as the PRTR Law). It is a material that should not be used from the environmental point of view.

A DETDA cross-linked urethane waterproof material using diethyltoluenediamine (hereinafter referred to as DETDA), which is a highly reactive aromatic polyamine, as an active hydrogen in the curing agent has been developed. This method has good low-temperature curability because DETDA is highly reactive, but there is a problem in securing the pot life in summer, and a method using a main agent using a special TDI (Patent Document 1) , A method in which isophorone diisocyanate (hereinafter referred to as IPDI), which is a low-reactivity polyisocyanate, is used in combination (Patent Document 2), and 4,4 ′, which is a mild aromatic secondary amine reactive to a curing agent. A method of using methylenebis (N-sec-butylaniline) in combination (Patent Document 3) has been proposed.
However, the waterproofing material using DETDA as active hydrogen is essentially insufficient in securing the usable time in summer, and there is a problem in the summer use of the waterproofing material for start-up that requires a long usable time. ing. However, the DETDA cross-linkable waterproofing material does not need to use MOCA, which is a specific chemical substance, as the curing agent, and since the physical properties are ensured even if the NCO content is low, the free TDI content is 1% by mass or less. Therefore, the specialization rule is not applicable, and even if lead carboxylate is not used, there is no problem in curability and foamability, so that it is a waterproof material superior to the MOCA cross-linked type in terms of environment.

The two-pack type hand-painted urethane waterproof material as described above is a high extension type of JIS A 6021, a waterproof coating material for buildings, and has durability such as mechanical strength, heat resistance, alkali resistance, acid resistance, and weather resistance. The performance is finely defined, and if it does not satisfy this standard, it will not be adopted by government offices, and of course, it will not be accepted as a product.
In addition, as the two-component urethane waterproofing material for hand-painting, there are 1/1 products and 1/2 products with a mixing ratio (mass ratio) of the main agent and the curing agent, but 1/2 products which are low in price. It is a general-purpose product. The 1/2 product is an increase in the amount of hardener by increasing the amount of plasticizers and fillers, but at a low price, the concentration of active hydrogen is low, so it meets JIS standards and is practically durable. Ensuring safety is an important issue.

Conventional two-component urethane waterproof materials have not been easy to ensure sufficient pot life in midsummer, not only for DETDA crosslinked waterproof materials but also for MOCA crosslinked waterproof materials.
In order to secure the pot life in midsummer with MOCA cross-linked waterproofing material, it is necessary to reduce lead carboxylate which is an accelerator, but if lead carboxylate which suppresses reaction with moisture is reduced, foaming will occur The problem of becoming intense occurs. For this reason, even with MOCA cross-linked waterproof materials that are mildly reactive and have good workability around 23 ° C, there is a limit to how long the pot life can be secured in summer. The current situation is that it is used by construction and management at the construction site, such as the method of construction in the early morning or evening when the target temperature is low, or the subdivision work is performed more frequently than usual. In particular, it is a heavy burden at the construction site to use a waterproofing material for rising, which requires a longer pot life than that for a flat place, in midsummer.

On the other hand, at a low temperature, the problem remains that it is difficult to sufficiently improve the curability of the MOCA crosslinked waterproof material. Originally, the reaction between MOCA and TDI prepolymer is low in reactivity at low temperatures, and further, when the promoting effect by lead carboxylate is close to 5 ° C., the efficiency tends to be impaired. Moreover, when lead carboxylate is excessively added, thermal deterioration of the coating film is promoted by the excessive lead carboxylate, resulting in a coating film having poor heat resistance. Also, carboxylic acid accelerators such as 2-ethylhexanoic acid are effective for promoting the reaction with MOCA, but have no effect of promoting the reaction with polyol, so that the low temperature curability of the coating film is improved. There are limits.
On the other hand, the DETDA cross-linkable waterproof material has relatively good low-temperature curability, but the curability is lowered in severe winters around 5 ° C. At that time, the curability is improved by adding lead 2-ethylhexanoate or 2-ethylhexanoic acid as an accelerator, but at the same time the pot life is increased, so that the workability is deteriorated. It is left.

Japanese Patent No. 3114557 Japanese Patent No. 395779 Japanese Patent No. 3445364

  The conventional blending technology for two-component urethane waterproofing materials has no problems in practicality such as finish and physical properties, and there is a limit to the technology to ensure sufficient pot life required for construction in summer. there were. In winter, the use of accelerators improves the curability to some extent, but the usable time is shortened and the workability deteriorates. There has been insufficient study of a versatile waterproof material that has no problem in curability while maintaining time. In addition, currently used waterproofing materials often contain components corresponding to specialization rules and lead compounds such as lead carboxylate, and a general-purpose waterproofing material that is more environmentally friendly and has good workability is desired. ing.

In the present invention, a versatile urethane waterproof material that has a longer usable time than the conventional one in the summer and does not cause problems in construction such as a foaming phenomenon and a pinhole has been studied. As a result, IPDI is used as the polyisocyanate component of the main agent, a prepolymer having a specific NCO content is used, and an aromatic polyamine containing DETDA as the active hydrogen of the curing agent is used for the plasticizer in the summer. It has been found that a waterproof material with good workability that does not cause foaming can be obtained while ensuring a longer pot life.
Furthermore, by selecting a specific accelerator for the waterproofing material that can ensure the above-mentioned pot life, it is possible to make it a curable waterproof material with sufficient pot life even in winter. It has been found that the urethane waterproof material can be used universally while ensuring sufficient pot life through it and at the same time appropriately controlling the curability.

The present invention includes the following aspects.
[1] A two-pack type urethane waterproofing composition for hand-painting comprising a main agent containing an isocyanate group-terminated prepolymer comprising a polyisocyanate and a polyol and a curing agent containing an aromatic polyamine, a plasticizer and an inorganic filler. And
The main component polyisocyanate contains isophorone diisocyanate, the main agent polyol contains polyoxyalkylene polyol, and the NCO content of the isocyanate group-terminated prepolymer of the main agent is 1.2 mass% or more and 4.5 mass% or less. Yes,
The curing agent, 70 equivalent% or more of the total active hydrogen is an aromatic polyamine, the aromatic polyamine contains diethyltoluenediamine, contains 20 to 80% by weight of inorganic filler,
The plasticizer is blended in the curing agent or in both the main agent and the curing agent so as to be 16 to 90% by mass with respect to the prepolymer in the main agent,
A two-component urethane waterproof material composition for hand-painting, wherein the ratio of the amino group amount (milli equivalent) of the aromatic polyamine to the plasticizer amount (g) is 0.6 or more and less than 1.6.
[2] The urethane waterproof material composition for two-pack type hand-painting according to [1], wherein the NCO content of the main agent is 1.5% by mass or more and 3.3% by mass or less.
[3] The two-component urethane waterproof material composition for hand-painting according to [1] or [2], wherein more than 70 equivalent% of the polyisocyanate is isophorone diisocyanate.
[4] The urethane waterproof material composition for two-component hand-painting according to any one of [1] to [3], wherein more than 50 equivalent% of the main component polyol is a polyoxyalkylene polyol.
[5] The two-component urethane waterproof material composition for hand-painting according to any one of [1] to [4], wherein more than 50 equivalent% of the aromatic polyamine is diethyl toluenediamine.
[6] selected from the group consisting of organic stannic compounds, carboxylic acid metal salts, carboxylic acids, acid anhydrides and tertiary amines as accelerators in the main agent, curing agent or mixture of main agent and curing agent The two-component urethane waterproof material composition for hand-painting according to any one of [1] to [5], wherein at least one kind is blended.
[7] Any one of [1] to [6], wherein at least one selected from the group consisting of a carboxylic acid metal salt, a carboxylic acid and an acid anhydride is blended in the curing agent as a curing accelerator. Two-component urethane waterproofing material composition for hand-painting as described in 1.
[8] Any one of [1] to [6], wherein at least one selected from the group consisting of an organic stannic compound and a tertiary amine is blended in the curing agent as a moisture curing accelerator. 2. A urethane waterproof material composition for hand-painting as described in 2.
[9] The isocyanate group-terminated prepolymer of the main agent has an NCO content of more than 3.3% by mass and 4.5% by mass or less, and diethyltoluenediamine and 4,4′-methylenebis as aromatic polyamines in the curing agent. The urethane waterproof material composition for two-pack type hand-painting according to any one of [1] to [8], comprising (N-sec-butylaniline) in an equivalent ratio of 51/49 to 97/3.
[10] The two-component hand-painted urethane waterproofing according to any one of [1] to [9], after the primer layer is applied to the adherend, or after the primer layer and the waterproof layer are applied. A urethane waterproofing method including a step of applying a material composition.
[11] The two-pack type hand according to any one of [1] to [9], after applying a ventilation cushioning sheet, a polymer sheet, a root-proof sheet or a polymer coating material to the adherend. A urethane waterproofing method including a step of applying a waterproofing composition for coating.

  The urethane waterproof material for hand-painted two-component type of the present invention can greatly extend the pot life without causing problems such as foaming during use in summer, and an accelerator is selected in winter By doing so, it is possible to obtain a waterproof material with good low-temperature curability while maintaining the pot life, and to provide a waterproof material with good workability throughout the year. Furthermore, since a specific chemical substance is not used as a raw material and a lead compound is not used as an accelerator, it is an excellent environment-friendly waterproof material.

(Main agent NCO content)
First, a detailed study was conducted on a summer formulation that particularly requires pot life. In general, in order to ensure the pot life, it is effective to reduce the NCO content of the main agent and correspondingly reduce the active hydrogen of the curing agent, but by reducing the active hydrogen, Further, there arises a problem that durability required as a urethane waterproof material such as strength, heat resistance and alkali resistance is lowered. In addition, in the MOCA cross-linked waterproof material, it is effective to reduce the lead carboxylate as an accelerator in order to ensure the pot life, but if lead carboxylate is reduced, the foaming prevention effect under high temperature and high humidity As a result, there was a limit to securing the pot life in summer.

  However, it can be seen that the urethane waterproof material of the present invention can ensure the strength and durability required for the urethane waterproof material even in a region where the NCO content is relatively low, and is difficult to cause a foaming phenomenon even in summer. It was. In a MOCA cross-linked waterproof material with a compounding ratio of main agent and curing agent that is a general-purpose product of 1/2 (mass ratio), it is practical unless the NCO content of the main agent is about 3.5 to 4.5% by mass. In general, it is difficult to be a waterproof material, but in the present invention, the NCO content of the main agent is in the range of 1.2 mass% to 4.5 mass%, so that a sufficient pot life is obtained. In addition, the strength and durability required for the urethane waterproof material can be ensured.

  The NCO content is preferably 1.2% by mass or more and less than 3.5% by mass, from 1.3% by mass to 3.3% by mass from the viewpoint of securing the pot life and the workable time. More preferably, it is more preferably 1.5% by mass or more and 3.2% by mass or less. In addition, when the NCO content is in the range of more than 3.3% by mass and 4.5% by mass or less, aromatic polyamines and polyols that are less reactive than DETDA as active hydrogen in the curing agent in order to ensure pot life. Is preferably used in combination. If the NCO content is less than 1.2% by mass, it is difficult to ensure the strength and durability required for the urethane waterproof material, and if it is 4.5% by mass or more, it is difficult to ensure the pot life.

(Main agent NCO group / OH group equivalent ratio)
In a conventional main agent using TDI as a polyisocyanate, the NCO group / OH group equivalent ratio, which is the ratio of the isocyanate group during production to the OH group of the polyol, is generally around 2.0. In the present invention, the range is preferably from 1.4 to 2.7, more preferably from 1.5 to less than 2.5, and most preferably from 1.6 to less than 2.3. Unlike the main agent using conventional TDI, the reaction can be completed easily even when the NCO group / OH group at the time of manufacture is around 1.5, and a main agent with relatively low viscosity and good storage stability is manufactured. can do.
In addition, when the NCO group / OH group equivalent ratio is less than 1.4, the thickening becomes severe, and when it exceeds 2.7, the free IPDI increases, and the working life and the physical properties are adversely affected.

(Polyisocyanate)
The present invention needs to contain IPDI as the polyisocyanate, and 70 equivalent% or more of the polyisocyanate is preferably IPDI, more preferably 80 equivalent% or more, and 90 equivalent% or more. Most preferred. When the IPDI is less than 70 equivalent%, it is difficult to obtain a waterproof material having a sufficient physical property and a sufficient working life.
In addition, some other polyisocyanates can be used in combination. As the isocyanate that can be used in combination, an aliphatic or alicyclic polyisocyanate having a mild reactivity is preferable. Hexamethylene diisocyanate, norbornene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate. Nert, hydrogenated diphenylmethane diisocyanate, hydrogenated tetramethylxylylene diisocyanate and the like. Aromatic polyisocyanates such as TDI, xylylene diisocyanate, and tetramethylxylylene diisocyanate can also be used, but TDI is a specified chemical substance in the Industrial Safety and Health Act and is preferable from the environmental aspect. Absent. On the other hand, derivatives with more than two functionalities such as IPDI nurate and trimethylolpropane (TMP) adducts have been commercialized, but many of them cannot be used because they tend to constrain the elongation, and are one of all polyisocyanates. It is preferable to use in the range of ˜30 equivalent%.

(Main component polyol)
The polyol used for the main agent needs to contain a polyoxyalkylene polyol, and more than 50 equivalent% of all polyols are preferably polyoxyalkylene polyols, and more preferably more than 70 equivalent%. When the polyoxyalkylene polyol is 50 equivalent% or less, it is difficult to ensure low viscosity with excellent workability. The polyoxyalkylene polyols are preferably polyoxypropylene polyols and polyoxyethylene propylene polyols having a molecular weight of 300 to 8000 which have no crystallinity, low viscosity and excellent economic efficiency. In addition, polyoxypropylene polyol in which a part of OH groups is primaryized can also be used.

  Other high molecular weight polyols such as polyester can be used as long as they are a part. Furthermore, short chain polyols such as 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, propylene glycol, and dipropylene glycol can be used in combination.

  As the polyol, the diol alone tends to be insufficient in heat resistance and alkali resistance, and if the polyol having a functional group number of triol or more is too large, it is difficult to ensure the pot life and elongation rate. The / triol equivalent ratio is preferably 98/2 to 10/90, more preferably 95/5 to 20/80, and most preferably in the range of 90/10 to 30/70.

(Synthesis of main agent)
Although it is a method for synthesizing isocyanate group-terminated prepolymers, it is preferable to use a reaction accelerator because the reaction is difficult to accelerate by simply heating. Common urethanization accelerators can be used, but organic stannic catalysts such as dibutyltin dilaurate and dioctyltin dilaurate are preferable, and the reaction can be efficiently performed with a small amount of addition of 0.0001 to 0.1% by mass. Can be promoted. The reaction temperature is preferably 60 to 100 ° C., and the reaction can be completed in about 2 to 6 hours. In addition, after completion | finish of reaction, it is more preferable to deactivate the reaction accelerator with phosphoric acid etc.

(Active hydrogen in curing agent)
In the present invention, it is necessary that more than 70 equivalent% of the active hydrogen in the curing agent is an aromatic polyamine, preferably more than 80 equivalent%, and most preferably more than 90 equivalent%. Polyols can be used in combination as active hydrogen, but since polyols are less cohesive than aromatic polyamines, it is possible to ensure the strength and durability required for waterproofing materials when the aromatic polyan content is 70 equivalent% or less. It becomes difficult.
Moreover, it is preferable that more than 50 equivalent% in aromatic polyamine is DETDA, it is more preferable that it is more than 70 equivalent%, and it is most preferable that it is more than 80 equivalent%. If DETDA is highly cohesive, highly reactive, liquid and soluble, and does not exceed 50 equivalent%, a waterproof material with good curability and high physical properties cannot be obtained.

  In addition, as an aromatic polyamine that 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, Kayahard AA (4,4'-methylenebis (2-ethylaniline)) manufactured by Nippon Kayaku Co., Ltd., Kayabond C-300 (4,4'-methylenebis (2,6-diethylaniline) manufactured by Nippon Kayaku Co., Ltd.) ), Kayabond C-400 (4,4′-methylenebis (2,6-diiso-propylaniline)) manufactured by Nippon Kayaku Co., Ltd., and the like. Further, although it is a low-reactivity aromatic polyamine, Albemarle Etacure 420 (4,4′-methylenebis (N-sec-butylaniline)), Albemarle Etacure 300 (dimethylthiotoluenediamine), Ihara Elastomer 650P (polytetramethylene glycol bis (p-aminobenzoate)) manufactured by Chemical Co., Ltd., Porea SL-100A (poly (tetramethylene / 3-methyltetramethylene ether) glycol bis (4-amino) manufactured by Ihara Chemical Co., Ltd. Benzoate)) etc. can be used. Among them, Etacure 420 is not as highly agglomerated as DETDA, but it has the effect of extending the pot life because of its low reactivity, and it is characterized by the fact that it does not deteriorate the curability so much, so it is particularly preferably used. be able to.

  As the polyol used in combination as the active hydrogen of the curing agent, general polyols used in urethane resins can be used, but polyols having a molecular weight of less than 1500 are preferable, and 1,3-propanediol, 2-methyl- 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, ethylene glycol, diethylene glycol, dipropylene glycol, tripropylene Examples include relatively high-cohesive polyols such as short-chain polyols such as glycol, polyester polyols, and polycarbonate polyols. Among them, primary hydroxyl group polyol is more preferable because it has high reactivity and is less likely to remain unreacted. Among them, 1,3-propanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, and molecular weight 300-800 aromatic-containing polyester polyols are more preferable for increasing the strength. The aromatic polyester polyol is preferably a liquid product using a low crystalline polyol such as Kuraray Polypol (manufactured by Kuraray Co., Ltd.).

  A polyol having a molecular weight of 1500 or more can also be used, and examples thereof include low viscosity polyoxypropylene polyol, polyoxyethylene propylene polyol, and polyester polyol. However, a polyol having a molecular weight of less than 1500 tends to be less likely to deteriorate the physical properties than a polyol having a molecular weight of 1500 or more, so that it can be used more preferably.

(Amino group equivalent per plasticizer)
In the present invention, the amount of amino groups (milli equivalents) of the aromatic polyamine containing DETDA and the plasticity are used in order to exhibit the strength and durability required for the urethane waterproof material while ensuring sufficient pot life. The ratio with respect to the amount of the agent (g), amino group (milli equivalent) / plasticizer (g) (hereinafter also referred to as “amino group equivalent per plasticizer”) must be 0.6 or more and less than 1.6. is there. When the “amino group equivalent per plasticizer” exceeds 1.2, it is preferable to partially use an aromatic polyamine or polyol having a reactivity lower than that of DETDA in order to ensure a usable time. If the "amino group equivalent per plasticizer" exceeds 1.6, it will be difficult to secure sufficient pot life, and at the same time, it will be disadvantageous in terms of economy, and if it is less than 0.6, it will be required for urethane waterproofing materials. The strength and durability cannot be demonstrated.

(Isocyanate group / aromatic amino group equivalent ratio)
In addition, since the strength and durability required for the urethane waterproof material largely depend on the amount of aromatic polyamine in the curing agent, the isocyanate group / aromatic amino group equivalent ratio is 0.8 to 1.6. Preferably, the range is 0.9 to 1.5, more preferably 0.95 to 1.4. If the isocyanate group / aromatic amino group equivalent ratio is less than 0.8, the aromatic amino group is excessive, resulting in insufficient high molecular weight of the cured product, resulting in low physical properties. Decreases, the strength and durability become insufficient, and the curability decreases.

(Plasticizer)
In the present invention, the use amount of the plasticizer is required to be 16 to 90% by mass with respect to the prepolymer component in the main agent, and is 20 to 85% by mass from the viewpoint of securing the pot life and physical properties. Preferably, it is 25-80 mass%. If the amount of plasticizer is less than 16% by mass, it will not be an economical urethane waterproof material with sufficient pot life, and if it exceeds 90% by mass, the required strength and durable physical properties will be ensured. And the bleed out of the plasticizer becomes severe. In principle, the plasticizer is blended with the curing agent, but it can be partially blended with the main agent.

  As a plasticizer used by this invention, the plasticizer which can be mix | blended generally with a urethane resin can be used. Examples include phthalates such as diisononyl phthalate (DINP), dioctyl phthalate (DOP), butyl benzyl phthalate (BBP), aliphatic dibasic acid esters, phosphate esters, trimellitic acid esters, sebacic acid esters , Epoxy fatty acid esters, glycol esters, animal and vegetable oil fatty acid esters, petroleum / mineral oil plasticizers, alkylene oxide polymerization plasticizers, and the like. Among them, diisononyl phthalate (DINP) and dioctyl phthalate (DOP), which have a flash point of 200 ° C. or more, are less likely to cause a decrease in mass over the long term, are aromatic polyesters, and are difficult to cause hydrolysis, and therefore are preferably used. it can. In addition, although a solvent can be used in the curing agent, there is a risk of shrinkage due to volatilization after construction, and the inorganic filler tends to settle, and there is an environmental problem. Is preferably used within the range, and more preferably not used.

(Inorganic filler)
Moreover, this invention needs to mix | blend 20-80 mass% of inorganic fillers with a hardening | curing agent. Urethane waterproof material without reinforcing effect of inorganic filler is not efficient to ensure the required strength, and by adding inorganic filler, it should be a versatile waterproof material with excellent economic efficiency it can. If the inorganic filler is less than 20% by mass, the reinforcing effect is insufficient and the economical efficiency is impaired, and if it exceeds 80% by mass, the thickening becomes intense and the workability deteriorates.
In the present invention, a relatively large amount of plasticizer is blended on the curing agent side, so that a large amount of inorganic filler can be blended, thereby enabling a blending ratio 1/2 (mass ratio) of the main agent / curing agent. Therefore, it can be used as a versatile waterproof material excellent in economic efficiency, and the strength and durability required for the urethane waterproof material can be sufficiently cleared after securing the pot life. Can be made urethane waterproof material.

  As the inorganic filler, calcium carbonate is preferred. Calcium carbonate has a high economic effect, has good dispersibility when producing a curing agent, has little viscosity increase even when blended in a large amount, and can easily reduce sedimentation during storage of the curing agent. The reinforcement effect is also high. Calcium carbonate includes various calcium carbonates such as heavy acid calcium carbonate, light calcium carbonate, and surface-treated colloidal calcium carbonate, and any calcium carbonate can be used. In particular, by using a surface waterproofing material with thixotropy imparted by a surface-treated colloidal calcium carbonate, it is possible to provide a waterproof material with good workability that has sufficiently secured the pot life in the summer.

  Moreover, a part of inorganic fillers such as silica, kaolin, talc, bentonite, aluminum hydroxide, barium hydroxide can be used. In addition, although the above inorganic filler contains adhering water, and this adhering water seems to react with an isocyanate group gradually, it is common that the adhering water is not regarded as active hydrogen. In addition, moisture (moisture) that is involved when mixing the main agent and curing agent, and moisture (moisture) that is absorbed from the coating film surface after applying a waterproofing material are generally considered to react to some extent with isocyanate groups. It is.

(Moisture curing accelerator)
In a two-pack type urethane waterproof material, it is common to use an isocyanate group in excess of active hydrogen. Even if the mixing ratio of the main agent and curing agent deviates to some extent at the time of construction, if the isocyanate group is excessive, high molecular weight can be achieved by self-crosslinking of the isocyanate group, and physical properties and durability can be ensured. When hydrogen is excessive, the terminal becomes active hydrogen, and no more can be cross-linked, so that it stops at a low molecular weight, and physical properties and durability are deteriorated. Further, when the isocyanate group is excessive, the adhesion between waterproof materials and the adhesion between the primer and the waterproof material are often improved. In that case, since the waterproof material using the conventional TDI prepolymer has a relatively fast reaction with moisture, for example, the active hydrogen is only an aromatic polyamine and the isocyanate group / aromatic amino group (equivalent ratio) is 1. Even when 2 and the isocyanate group are excessive, the excess isocyanate group and the water react almost within one week (temperature 23 ° C./humidity 50%) and reach the maximum strength.

However, in the present invention using an IPDI prepolymer, the reaction between excess isocyanate groups and moisture is slow, so that it may take one week or more to reach the maximum strength (temperature 23 ° C./humidity). 50%). However, since the reaction with DETDA proceeds promptly, there is no problem in curability (workable time) until the next day.
However, when the strength development is slow, the follow-up ability to the crack of the ground concrete is also slowed, and the risk of being deteriorated by acid, alkali, ultraviolet rays, etc. before the strength development is increased. As a result of investigations to improve this problem, it was found that when the isocyanate group / aromatic amino group equivalent ratio is excessive, the moisture curing accelerator is preferably used. In particular, it is effective to be used when the isocyanate group / aromatic amino group equivalent ratio is 1.05 or more, more effective when 1.1 or more, and most effective when 1.2 or more. I found out. Conventional waterproofing materials using TDI prepolymers are generally not used because the foaming properties become severe when a moisture curing accelerator is used, but waterproofing materials using IPDI prepolymers increase foaming properties. As a result, it was found that the strength could be increased quickly and the waterproofing material had high physical properties and good durability.

In the present invention, a general moisture curing accelerator can be used, and among these, organic stannic compounds and tertiary amines are preferred. Since any accelerator hardly accelerates the reaction with the aromatic polyamine, the strength expression can be accelerated without shortening the pot life. Tertiary amines are more preferred moisture curing accelerators because they do not promote thermal degradation. Further, among tertiary amines, an imidazole compound is most preferable because it has less foaming properties and can easily control moisture curing acceleration.
Examples of organic stannic compounds include dibutyltin oxide, dioctyltin oxide, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin di-2-ethylhexanoate, dioctyltin diacetate, dioctyltin dilaurate, dibutyltin dimercaptaide, dibutyl Examples thereof include tin bisacetylacetonate, dibutyltin oxylaurate, dioctyltin dineodecanate, dibutyltin bisbutylmalate, dioctyltin 2-ethylhexylmalate, and among them, dibutyltin dilaurate and dioctyltin dilaurate are preferable. The organic stannic compound is preferably used in an amount of 0.001 to 0.1% by mass in the curing agent.

As the tertiary amine, for example, general tertiary amines such as triethylamine, tributylamine, triethylenediamine, N-ethylmorpholine, bis (2-morpholinoethyl) ether, diazabicycloundecene and the like can be used. Examples of the imidazole compound include substituents at the 1- and 2-positions such as 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-benzyl-2-methylimidazole, and 1-benzyl-2-phenylimidazole. And compounds having a substituent at the 1-position such as 1-methylimidazole and 1-allylimidazole can be used. Among them, an imidazole compound having substituents at the 1-position and the 2-position is more preferable because of its high strength expression promoting effect. The tertiary amine is preferably used in an amount of 0.01 to 2.0% by mass in the curing agent. In addition, although a moisture hardening accelerator can also be mix | blended in a main ingredient, since there exists a danger of impairing storage stability, it is preferable to mix | blend with a hardening | curing agent.
As described above, the present invention provides a urethane waterproof material that has a longer working life than conventional urethane waterproof materials and is suitable for the summer without foaming.

(For winter)
Unlike the conventional two-pack type urethane waterproof material, the present invention has an advantage that it is an environmentally-friendly waterproof material that does not use a specific chemical substance as a main agent and a curing agent.
At low temperature, when the NCO content of the main agent is low, the workable time becomes long. Therefore, the NCO content is preferably 1.5% by mass or more and 4.5% by mass or less, and 1.8% by mass or more. It is more preferably 4.0% by mass or less, and most preferably 2.0% by mass or more and less than 4.0% by mass.
Since the reaction between the IPDI prepolymer and DETDA is slow at low temperatures, it is preferable to use a curing accelerator. As a result of the examination, it was found that the carboxylic acid metal salt and the carboxylic acid have a curing accelerating property and can be cured the next day even at low temperatures. However, since any curing accelerator tends to shorten the pot life and deteriorates the workability, it is necessary to pay attention to the amount used.
Examples of carboxylic acid metal salts include 2-ethylhexanoic acid, neodecanoic acid, naphthenic acid, oleic acid, linoleic acid, linolenic acid, lead salts of resin acids, zinc salts, bismuth salts, zirconium salts, tin salts, copper salts, A magnesium salt, a calcium salt, a strontium salt, a barium salt, etc. are mentioned. Among these, calcium carboxylate, bismuth carboxylate, and zinc carboxylate are preferable, and zinc carboxylate is most preferable because it has high curing acceleration and hardly causes thermal deterioration. In addition, in the waterproof material using the conventional TDI prepolymer, zinc carboxylate was not normally used since it has foamability. On the other hand, lead carboxylate is also effective, but is not preferable because of environmental restrictions. Carboxylic acid metal salts also serve as moisture curing accelerators to a certain extent and shorten the pot life. However, when polyols are used in combination with curing agents, the reaction with NCO is promoted, so they are also used in summer formulations. Sexual adjustments can be made. It is preferable to use 0.1 to 4.0% by mass of the carboxylic acid metal salt in the curing agent.

Examples of the carboxylic acid include propionic acid, 2-methylpentanoic acid, 2-ethylhexanoic acid, isononanoic acid, and naphthenic acid. Among them, 2-ethylhexanoic acid is preferable. The carboxylic acid is preferably used in an amount of 0.05 to 2.0% by mass in the curing agent.
Carboxylic acid does not show moisture curing acceleration, but can effectively promote the reaction with aromatic polyamines such as DETDA even at low temperatures. Moreover, although pot life is shortened, it can be used for summer blending to adjust curability.

(Acid anhydride curing accelerator)
As a result of further investigation, it was found that acid anhydrides are more preferable as curing accelerators. When acid anhydride is added to the curing agent in advance, it shows almost the same curing acceleration as carboxylic acid, but when it is added to the main agent or when the main agent is mixed with the curing agent, the pot life is increased. The curability can be promoted without significantly shortening.
This phenomenon is considered that acid anhydrides are added with active hydrogen groups such as amino groups, hydroxyl groups and moisture in the curing agent to generate carboxylic acids, and the generated carboxylic acids are considered to exhibit curing acceleration properties. The addition reaction with is expected not to be instantaneous, but to proceed at an appropriate reaction rate, and as a result, it has little influence on the pot life and is considered to show the potential for excellent curability.

By using an acid anhydride that shows the potential as a curing accelerator for a waterproofing compound that can take a longer pot life than in the past, it is possible to ensure a sufficient pot life even in the summer season. It was also found that a full-year type waterproofing material having a fast curing property that can be applied the next day even at low temperatures is possible. Therefore, in this invention, the method of adding an acid anhydride to a main ingredient or when mixing a main ingredient and a hardening | curing agent is preferable. The method of adding an acid anhydride when mixing the main agent and the curing agent includes a main agent part containing an isocyanate group-terminated prepolymer, a curing agent part containing an aromatic polyamine, a plasticizer and an inorganic filler, and an acid anhydride. A method of preparing a kit comprising curing accelerator parts including an object and mixing those parts at a construction site can be exemplified.
When an acid anhydride is added to the main agent, the acid anhydride can remain stable because there is no active hydrogen group in the main agent, and the addition reaction of the acid anhydride starts when mixed with the curing agent. The effect as a potential promoter can be exhibited. Moreover, when adding when mixing a main ingredient and a hardening | curing agent at a construction site as a 3rd component, since complicated work, such as a subdivision and a lightweight, is accompanied, it is more preferable to mix | blend an acid anhydride with a main ingredient.
In addition, since an acid anhydride can also not shorten a pot life so much, it can also be used for summer mixing | blending and can adjust sclerosis | hardenability.

Examples of the acid anhydride used in the present invention include acetic anhydride, propionic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, 3-methyl- 1,2,3,6-tetrahydrophthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, hexahydrophthalic acid Anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride, bicyclo [2.2.1 ] Heptane-2,3-dicarboxylic acid anhydride, methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic acid anhydride, ethylene glycol bisanhydro trimellitate Glycerin bisanhydro trimellitate monoacetate, tetrapropenyl succinic anhydride, octenyl succinic anhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,3,3a, 4,5 , 9b-Hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione, 1,2,3,4-butanetetracarboxylic dianhydride Etc.
An acid anhydride may be used independently or 2 or more types may be used together.

  Since the two-component urethane waterproofing material is applied by mixing the main agent and the curing agent at the construction site, the acid anhydride that is solid at room temperature may be crystallized without being completely dissolved in the mixed solution. When the acid anhydride is crystallized, a sufficient curing accelerating effect may not be obtained. Therefore, an acid anhydride that is liquid at room temperature is preferable. Examples of acid anhydrides that are liquid at room temperature include acetic anhydride, propionic anhydride, succinic anhydride, and HN-2200 (3-methyl-1,2,3,6-tetrahydrophthalic anhydride manufactured by Hitachi Chemical Co., Ltd. And 4-methyl-1,2,3,6-tetrahydrophthalic anhydride), Rikacid HH (Hexahydrophthalic anhydride) manufactured by Shin Nippon Rika Co., Ltd., Rikacid MH manufactured by Shin Nippon Rika Co., Ltd. -700 (mixture of 3-methylhexahydrophthalic anhydride / 4-methylhexahydrophthalic anhydride = 70/30), Ricacid MH (4-methylhexahydrophthalic anhydride) manufactured by Shin Nippon Rika Co., Ltd. Rikacid HNA-100 (Methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride and bicyclo [2.2.1] manufactured by Shin Nippon Chemical Co., Ltd. A mixture of pentane-2,3-dicarboxylic anhydride), MHAC-P (methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride) manufactured by Hitachi Chemical Co., Ltd., Sanyo Chemical Examples include DSA (tetrapropenyl succinic anhydride) manufactured by Kogyo Co., Ltd., Ricacid OSA (octenyl succinic anhydride) manufactured by Shin Nippon Rika Co., Ltd., etc., among which HN-2200 (3- Methyl-1,2,3,6-tetrahydrophthalic anhydride and a mixture of 4-methyl-1,2,3,6-tetrahydrophthalic anhydride), Hitachi Chemical Co., Ltd. MHAC-P (Methyl-3 , 6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride), Rikacid MH-700 (3-methylhexahydrophthalic acid) manufactured by Shin Nippon Chemical Co., Ltd. Mixtures of anhydride / 4-methyl-hexahydrophthalic anhydride = 70/30), Sanyo Chemical Industries Ltd. of DSA (tetrapropenyl succinic anhydride) are more preferable.

  As for the usage-amount of an acid anhydride, it is desirable to use 0.05-10.0g with respect to 100g of main ingredients, and it is still more desirable to use 0.1-5.0g. If the amount of the acid anhydride used is too small, sufficient fast curability cannot be obtained. On the other hand, if the amount is too large, sufficient pot life cannot be ensured and the physical properties deteriorate.

In the present invention, it is preferable to use an acid anhydride as the curing accelerator, but other curing accelerators can be used, and they can be used in combination with an acid anhydride.
Examples of other curing accelerators include organic stannic compounds, tertiary amines, carboxylic acid metal salts, and carboxylic acids.

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

(Main agent / curing agent ratio)
The mixing ratio of the main agent and the curing agent is not particularly limited, but is preferably in a range of 1/1 to 1/3, more preferably 1/1 to 1/2 in terms of mass ratio.

(Waterproofing method)
In addition, the two-component environmentally-friendly hand-painted urethane waterproof material of the present invention cannot be directly applied to an inorganic base such as concrete. In the case of an inorganic base, since it does not adhere to the urethane waterproof material, it can be applied after applying a primer capable of shielding the base water to some extent and ensuring adhesion. In addition, it can be applied with an intermediary primer on the existing urethane waterproof layer, including at the time of repair. Moreover, it can be applied after fixing a polymer sheet such as an air-permeable buffer sheet and a vinyl chloride sheet, a rubber sheet, and a non-woven sheet to the inorganic base with a primer, an adhesive, mechanical fixing, laying, and the like. 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 ensured, so that it can be applied after applying a dedicated primer.
The present invention is not intended to repair an asphalt waterproof layer, and is intended to waterproof and protect inorganic substrates such as concrete, metal substrates, polymer resin substrates, and rubber substrates. In addition, when the two-pack type environmentally-friendly hand-painted urethane waterproof material of the present invention is used in a portion where it is directly exposed to sunlight, it is a principle that a top coat is applied.

Raw materials The raw materials used in the following examples and comparative examples are as follows.
IPDI: VESTANAT (registered trademark) IPDI, isophorone diisocyanate alone, NCO content 37.8% by mass, NCO functional group number about 2.0, manufactured by Evonik Japan Co., Ltd. T-80: Coronate T-80, 2, 4 -Tolylene diisocyanate / 2,6-tolylene diisocyanate = 80/20 (mass ratio) mixture, NCO content 48.3 mass%, manufactured by Tosoh Corporation T-100: Coronate T-100, 2, 4 -Tolylene diisocyanate 100% product, NCO content 48.3 mass%, Tosoh Corporation Sannix PP-2000: polyoxypropylene diol, average molecular weight 2000, OH value 56.1mgKOH / g, Sanyo Chemical Industries Sanix GH-3000 manufactured by company: Polyoxypropylene triol, average molecular weight 000, OH value: 56.1 mgKOH / g, Sanyo Chemical Industries, Ltd. Sanniks GH-5000: Polyoxypropylene triol, average molecular weight 5000, OH value: 33.7 mgKOH / g, Sanyo Chemical Industries, Ltd. Sanniks GP -600: Polyoxypropylene triol, average molecular weight 600, OH value: 280.5 mg KOH / g, Sanyo Chemical Industries, Ltd. MC-2000 Solvent: normal paraffin, isoparaffin mixture, Sankyo Chemical Co., Ltd. Dioctyltin dilaurate: KS- 1200A-1, manufactured by Kyodo Yakuhin Co., Ltd. DETDA: Etacure 100, diethyltoluenediamine, Albemarle Japan Co., Ltd. MOCA: Iharacamine MT, 4,4'-diamino-3,3'-dichlorodiphenylmethane [Amine = 420 mgKOH / g], Etahure 420 manufactured by Ihara Chemical Industry Co., Ltd .: 4,4′-methylenebis (N-sec-butylaniline), aromatic secondary diamine, Elastomer 650P manufactured by Albemarle Co., Ltd .: polytetramethylene oxide-di-p -Aminobenzoate, average molecular weight 860, Porea SL-100A manufactured by Ihara Chemical Industry Co., Ltd .: Polytetramethylenemethyltetramethylene oxide-di-p-aminobenzoate, average molecular weight 1200, Kuraray polyol P-530 manufactured by Ihara Chemical Industry Co., Ltd .: Aromatic polyester diol obtained by reaction of 3-methyl-1,5-pentanediol and isophthalic acid, average molecular weight 500, OH value: 224.4 mg KOH / g, Kuraray Co., Ltd. Sanniks PP-400: Poly Oxypropylenediol, average molecular weight 400, OH value 280.5 mg KOH / g, Sanyo Chemical Industries, Ltd. 1,4-butanediol: Reagent, Nacalai Tesque Co., Ltd. DINP: Sunsosizer DINP, Diisononylphthalate, Shin Nippon Rika Co., Ltd. Manufactured calcium carbonate NS # 100: NS # 100, calcium carbonate, manufactured by Nitto Flour Chemical Co., Ltd. Calcium carbonate Calfine N-2: Calcium carbonate (surface treatment), manufactured by Maruo Calcium Co., Ltd. Additives: manufactured by Enomoto Kasei Co., Ltd. Dioctyltin dilaurate: KS-1200A-1, manufactured by Kyodo Yakuhin Co., Ltd. HN-2200: Tetrahydromethylphthalic anhydride, manufactured by Hitachi Chemical Co., Ltd. Lead 2-ethylhexanoate (Pb 20%): Nikka Octix Lead 20% TS, 2 -Lead ethylhexanoate and nor Malparaffin, mixture with isoparaffin mixture, 20% content as Pb, manufactured by Nippon Chemical Industry Co., Ltd. 1-isobutyl-2-methylimidazole: DABCO NC-IM, manufactured by Air Products Japan Co., Ltd. 2-ethylhexanoic acid: octylic acid, Toyo Gosei Kogyo Co., Ltd. 2-ethylhexanoate zinc (Zn8%): Nikka octix zinc 8% (T), a mixture of zinc 2-ethylhexanoate and mineral spirit, containing 8% as Zn, Nippon Kagaku Sangyo Co., Ltd. Company PACCAT B7 (Bi7%): A mixture of bismuth resinate and mineral spirit, containing 7% as Bi, MHAC-P manufactured by Nippon Chemical Industry Co., Ltd .: Methyl-3,6-endomethylene-1,2,3 6-tetrahydrophthalic anhydride, manufactured by Hitachi Chemical Co., Ltd. DSA: tetrapropenyl Succinic anhydride, manufactured by Sanyo Chemical Industries, Ltd.

Preparation of Main Agent According to the formulation 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. Thereafter, the mixture was reacted at 90 to 100 ° C. for 3 to 9 hours with stirring to obtain each main agent.

Preparation of curing agent In accordance with the formulation shown in Tables 1 to 14, the liquid material was charged into a metal container, mixed at a low speed with a stirrer (dissolver blade) and homogenized, and then mixed with calcium carbonate and mixed at 1500 rpm for 15 minutes. Obtained.

Examples 1 and 2 (Table 1 Representative examples of summer and winter (full-year) formulations)
In Examples 1 and 2, the main agent and the curing agent were obtained according to the formulation in Table 1. These main agents and curing agents were mixed at a mass ratio of 1: 2 to obtain a urethane waterproof material composition.
In Example 1, the pot life at 23 ° C. was 75 minutes, and the next day construction was possible while ensuring sufficient pot life as a summer formulation. The obtained coating film exhibited good initial physical properties and heat resistant physical properties as a highly stretchable urethane waterproof material for hand-painting.
In Example 2, in which 0.71% by mass of acid anhydride curing accelerator HN-2200 was added to the main component of Example 1, the pot life at 23 ° C. was 56 minutes. The next day construction was possible even at a low temperature of 5 ° C. while ensuring sufficient pot life. The obtained coating film exhibited good initial physical properties and heat resistant physical properties as a highly stretchable urethane waterproof material for hand-painting.

Comparative Examples 1 and 2 (Table 2 MOCA cross-linked waterproof material)
Comparative Examples 1 and 2 are examples of conventional MOCA cross-linked waterproof material compositions.
The main agent of Comparative Examples 1 and 2 using T-80 as the main polyisocyanate compound contained 1.48% by mass of T-80 as a specific chemical substance. In Comparative Example 1, the pot life at 23 ° C. is 60 minutes, and it can be applied the next day while securing sufficient pot life as a summer formulation. Although it shows good initial physical properties and heat-resistant physical properties as a urethane waterproof material, it is necessary to use 1.00 mass% of lead 2-ethylhexanoate (Pb20%), which is a specified type 1 designated chemical substance, as a curing accelerator. is there. In Comparative Example 2, which is a blend for winter using 1.50% by mass of lead 2-ethylhexanoate (Pb 20%), the curing was slow at the low temperature of 5 ° C. and it was difficult to apply the next day. Furthermore, the tensile strength ratio after heat treatment was as low as 71%.

Comparative Examples 3 and 4 (Table 2 DETDA cross-linked waterproof material)
Comparative Examples 3 and 4 are examples of DETDA crosslinked waterproofing material compositions using T-100, which is a special product, as the main polyisocyanate compound.
In Comparative Example 3 in which the active hydrogen compound in the curing agent is DETDA, the obtained coating film shows good initial physical properties and heat-resistant physical properties as a highly stretchable urethane waterproofing material for hand coating. The usage time was 43 minutes, which was insufficient as a summer formulation. In Comparative Example 4 using DETDA and Kuraray polyol P-530 as active hydrogen compounds in the curing agent, the pot life at 23 ° C. is 63 minutes, and the pot life is sufficient for summer use, but curing is not possible. The next day construction was impossible late. Furthermore, the tensile strength and tear strength of the obtained coating film were lower than the JIS standard for the highly stretchable urethane waterproof material for hand coating. Further, the initial physical property and the tensile strength ratio after the heat treatment were as low as 77%.

Comparative Example 5, Examples 3 and 4 (Table 3 Amino group equivalent per plasticizer)
Comparative Example 5 is an example in which the NCO group / OH group equivalent ratio was lowered by the diol / triol ratio of the same main agent as in Example 1 to make the main agent NCO content 1.53% by mass. In Comparative Example 5, the amino group equivalent per plasticizer was reduced to 0.50 meq / g, which was outside the claimed range of the present invention. As a result, the tensile strength and tear strength of the obtained coating film were high-extension type urethane waterproofing for hand coating. The material was below the JIS standard.
Example 3 in which the same main agent as Comparative Example 5 was used, the mixing ratio of the main agent and the curing agent was 1: 1.5, and 0.50% by mass of HN-2200, which is an acid anhydride curing accelerator, was added to the main agent. The amino group equivalent per plasticizer was 0.78 meq / g, which is within the scope of the present invention, and the next day construction was possible while securing sufficient pot life for summer blending. The obtained coating film exhibited good initial physical properties and heat resistant physical properties as a highly stretchable urethane waterproof material for hand-painting.
Example 4 in which the NCO group / OH group equivalent ratio of the main agent was increased so that the NCO content of the main agent was 4.02% by mass was 1.53 meq / g in which the amino group equivalent per plasticizer was within the scope of the present invention. As a result of using 20 equivalent% of low-reactivity Etacure 420 in addition to DETDA as an aromatic polyamine as a curing agent, the next day construction was possible while ensuring sufficient pot life as a summer formulation. . The obtained coating film exhibited good initial physical properties and heat resistant physical properties as a highly stretchable urethane waterproof material for hand-painting.

Examples 5 and 6 (Table 4 Main agent NCO content)
In Examples 5 and 6, the main agent and the curing agent were obtained according to the formulation in Table 4. The main agent and the curing agent were mixed at a mixing ratio shown in Table 4 to obtain a urethane waterproof material composition.
In Examples 5 and 6 in which the NCO content of the main agent is as low as 1.53% by mass and 1.98% by mass, respectively, HN-2200, which is a curing accelerator, is used as the main agent in an amount of 0.50% by mass and 0.78% by mass, respectively. As a result, the next day construction was possible while ensuring sufficient pot life as a summer formulation. The obtained coating film exhibited good initial physical properties and heat resistant physical properties as a highly stretchable urethane waterproof material for hand-painting.

Examples 7 to 11 (Table 5: main agent NCO / curing agent NH ₂ (equivalent ratio))
Examples 7-11 obtained the main ingredient and the hardening | curing agent according to the mixing | blending of Table 5. The main agent and the curing agent were mixed at a mass ratio of 1: 2 to obtain a urethane waterproof material composition.
The base NCO / curing agent NH ₂ (equivalent ratio) is 0.90, Example 8 of 1.05, Example 9 of 1.20, and Examples 10 and 11 of 1.30 are both high. As a stretchable hand-painted urethane waterproof material, it showed good film properties and was able to be applied the next day while ensuring sufficient pot life for summer use. In Example 7, where the main agent NCO / curing agent NH ₂ (equivalent ratio) is relatively low, 0.78% by mass of HN-2200, which is a curing accelerator, was used, and the main agent NCO / curing agent NH ₂ (equivalent ratio) was used. In Examples 9 and 10 having a relatively high value, 0.40% by mass of 1-isobutyl-2-methylimidazole, which is a moisture curing accelerator, was used. Further, in Example 11 in which the main agent NCO / curing agent NH ₂ (equivalent ratio) is relatively high 1.30 and no moisture curing accelerator is used, the curing is compared with Example 10 using the moisture curing accelerator. Although the physical properties of the coating film after one week were low, the physical properties of the coating film after two weeks were good values as a highly stretchable urethane waterproof material for hand-painting.

Examples 12-14 (Table 6 Main ingredient diol / triol equivalent ratio)
Examples 12 to 14 are examples in which the main component diol / triol equivalent ratio was changed from 70/30 of Example 1 to 80/20, 60/40, and 40/60, respectively. Examples 12 to 14 all showed good coating film properties as a highly stretchable urethane waterproof material for hand coating, and could be applied the next day while ensuring sufficient pot life as a summer formulation.

Examples 15 to 17 (Table 7 Main ingredient polyol winter formulation)
Example 15 is an example in which 0.69% by mass of the curing accelerator HN-2200 was added in the mixing of the main agent and the curing agent in the winter formulation of Example 2. In Example 15, the pot life at 23 ° C. was 48 minutes, and the next day construction was sufficiently possible even at a low temperature of 5 ° C. while ensuring a pot life sufficient for winter blending. The obtained coating film exhibited good initial physical properties and heat resistant physical properties as a highly stretchable urethane waterproof material for hand-painting.
Examples 16 and 17 are examples in which the main component diol / triol equivalent ratio was changed from 70/30 of Example 15 to 60/40 and 50/50, respectively. Examples 16 and 17 both show good coating film properties as a highly stretchable urethane waterproof material for hand coating, and can be applied the next day even at a low temperature of 5 ° C. while ensuring sufficient pot life as a winter formulation. there were.

Examples 18 to 20 (Table 8 Amount of acid anhydride curing accelerator used)
Examples 18 to 20 are examples in which the amount of the curing accelerator HN-2200 used was changed from 0.71% by mass of Example 2 to 0.47, 0.95, and 1.66% by mass, respectively. The pot life at 23 ° C. is 61 minutes, 52 minutes, and 38 minutes, respectively, while Examples 18 and 19 are used as summer / winter formulations, and Example 20 is used as a winter formulation while securing sufficient pot life. Construction was possible the next day even at a low temperature of 5 ° C. The obtained coating film exhibited good initial physical properties and heat resistant physical properties as a highly stretchable urethane waterproof material for hand-painting.

Examples 21 to 24 (Table 9 Various curing accelerators)
In Examples 21 to 24, the hardening accelerator was changed from HN-2200 of Example 15 to 0.20% by mass of 2-ethylhexanoic acid, 1.00% by mass of zinc 2-ethylhexanoate (Zn8%), and 2-ethylhexanoic acid. In this example, lead (Pb20%) is changed to 1.00% by mass and PACCAT B7 (Bi7%) is 1.00% by mass. The pot life at 23 ° C. was 38 minutes, 41 minutes, 37 minutes, and 38 minutes, respectively, and the next day construction was sufficiently possible even at a low temperature of 5 ° C. while securing sufficient pot life for winter blending. The obtained coating film exhibited good initial physical properties and heat resistant physical properties as a highly stretchable urethane waterproof material for hand-painting.

Examples 25 and 26 (Table 10 Various moisture curing accelerators)
Examples 25 and 26 are examples in which 0.50% by mass of 1-isobutyl-2-methylimidazole and 0.01% by mass of dioctyltin dilaurate were used in the summer formulation of Example 1, respectively. The pot life at 23 ° C. was 69 minutes and 73 minutes, respectively, and the next day construction was sufficiently possible while ensuring sufficient pot life as a summer formulation. The obtained coating film exhibited good initial physical properties and heat resistant physical properties as a highly stretchable urethane waterproof material for hand-painting.

Examples 27 to 29 (Table 11 Various acid anhydride curing accelerators)
Examples 27 to 29 are examples using 0.69% by mass of HN-2200, 0.74% by mass of MHAC-P, and 1.11% by mass of DSA, respectively, as the acid anhydride type curing accelerator. The pot life at 23 ° C. was 75 minutes, 87 minutes, and 123 minutes, respectively, and the next day construction was sufficiently possible while ensuring sufficient pot life for summer blending. The obtained coating film exhibited good initial physical properties and heat resistant physical properties as a highly stretchable urethane waterproof material for hand-painting.

Examples 30 to 32 (Table 12 Combined use of aromatic polyamines other than DETDA)
Examples 30-32 obtained the main ingredient and the hardening | curing agent according to the mixing | blending of Table 12. These main agents and curing agents were mixed at a mass ratio of 1: 2 to obtain a urethane waterproof material composition.
Example 30 in which 40 equivalent% of etacure 420 was used in addition to DETDA as an aromatic polyamine, Example 31 in which 20 equivalent% of Elastomer 650P was used, and Example 32 in which 20 equivalent% of Porea SL-100A were used were for summer use Construction was possible the next day while ensuring sufficient pot life as a formulation. The obtained coating film exhibited good initial physical properties and heat resistant physical properties as a highly stretchable urethane waterproof material for hand-painting.

Examples 33 to 35 (Table 13 Use of polyol as curing agent active hydrogen)
Examples 33-35 obtained the main ingredient and the hardening | curing agent according to the mixing | blending of Table 13. These main agents and curing agents were mixed at a mass ratio of 1: 2 to obtain a urethane waterproof material composition.
In addition to DETDA as a curing agent active hydrogen, Example 33 using 20 equivalent% of Sannics PP-400, Example 34 using 20 equivalent% of 1,4-butanediol, and 20 equivalent% of Kuraray polyol P-530 were used. In Example 35, the next day construction was sufficiently possible while ensuring sufficient pot life as a summer formulation. The obtained coating film exhibited good initial physical properties and heat resistant physical properties as a highly stretchable urethane waterproof material for hand-painting.

Examples 36-38 (Table 14 Waterproofing material for elevation)
Examples 36-38 obtained the main ingredient and the hardening | curing agent according to the mixing | blending of Table 14. These main agents and curing agents were mixed at a mass ratio of 1: 2 to obtain a urethane waterproof material composition.
Example 36 using 21.0% by mass, 24.0% by mass, and 27.0% by mass of Calfine N-2 of surface-treated colloidal calcium carbonate, respectively, in order to impart non-sag properties as a waterproofing material for an elevation surface As for -38, construction was possible enough on the next day, ensuring sufficient pot life and sagability as a composition for an elevation part summer. The obtained coating film exhibited good initial physical properties and heat resistant physical properties as a highly stretchable urethane waterproof material for hand-painting.

  In addition, the measuring method of each evaluation item is as follows.

[NCO (mass%)]
About 1 g of the main agent is precisely weighed in a 200 mL Erlenmeyer flask, and 10 mL of 0.5N di-n-butylamine (toluene solution), 10 mL of toluene and an appropriate amount of bromophenol blue are added to it, and then about 100 mL of methanol is added and dissolved. The mixture is titrated with 0.25N hydrochloric acid solution. NCO (mass%) is calculated | required by the following formula | equation.
NCO (mass%) = (blank titration value−0.5N hydrochloric acid solution titration value) × 4.202 × 0.25N hydrochloric acid solution factor × 0.25 ÷ sample mass

[Pot life (minutes)]
In the air circulation type environmental test chamber at 23 ° C and 50% humidity, the time from the start of stirring and mixing the main agent and curing agent at a predetermined ratio until the viscosity at 2 rpm with the BH viscometer reaches 60,000 mPa · s It was measured. In addition, in the waterproofing material for elevation parts, the time until the viscosity at 20 rpm reached 100,000 mPa · s was measured with a BH viscometer.

[Installable time (hours)]
Although 2 kg / m ^{2 of} a waterproof material in which the main agent and curing agent are stirred and mixed at a predetermined ratio in an air circulation type environmental test chamber at 23 ° C. or 5 ° C. and 50% humidity is not completely cured. The time when the person can walk with shoes and can start the next process is measured.

[Tensile strength (N / mm ² )]
Measurements were made based on JIS A 6021 for test pieces with curing conditions of 23 ° C. and humidity of 50% for 7 days or 14 days (23 days at 23 ° C. for JIS A 6021, 7 days unless otherwise specified). (The tensile strength is 2.3 N / mm ² or more in the urethane rubber high elongation type of JIS A 6021).

[Elongation at break (%)]
Measurements were made based on JIS A 6021 for test pieces with curing conditions of 23 ° C. and humidity of 50% for 7 days or 14 days (23 days at 23 ° C. for JIS A 6021, 7 days unless otherwise specified). (In the JIS A 6021 urethane rubber high elongation type, the elongation at break is 450% or more).

[Tear strength (N / mm)]
Measurements were made based on JIS A 6021 for test pieces with curing conditions of 23 ° C. and humidity of 50% for 7 days or 14 days (23 days at 23 ° C. for JIS A 6021, 7 days unless otherwise specified). (The tear strength is 14 N / mm or more in the urethane rubber type high elongation type of JIS A6021).

[Heat resistance Tensile strength ratio (%)]
After test for 7 days at 23 ° C and 50% humidity, the test piece was heated for 28 days in a dryer at 80 ° C (7 days at 80 ° C for JIS A 6021) and subjected to heat treatment according to JIS A 6021. The tensile strength ratio (%) with respect to the JIS A 6021 urethane rubber high-elongation type was 80% or more at 80 ° C. for 7 days.

  The composition of the present invention can be suitably used as a waterproof material for roofs of buildings, verandas of apartment houses such as condominiums, etc., as a highly stretchable two-component environment-friendly urethane waterproof material.

Claims (11)

A two-component hand-painted urethane waterproof material composition comprising a main agent containing an isocyanate group-terminated prepolymer comprising a polyisocyanate and a polyol and a curing agent comprising an aromatic polyamine, a plasticizer and an inorganic filler,
The main component polyisocyanate contains isophorone diisocyanate, the main agent polyol contains polyoxyalkylene polyol, and the NCO content of the isocyanate group-terminated prepolymer of the main agent is 1.2 mass% or more and 4.5 mass% or less. Yes,
The curing agent, 70 equivalent% or more of the total active hydrogen is an aromatic polyamine, the aromatic polyamine contains diethyltoluenediamine, contains 20 to 80% by weight of inorganic filler,
The plasticizer is blended in the curing agent or in both the main agent and the curing agent so as to be 16 to 90% by mass with respect to the prepolymer in the main agent,
A two-component urethane waterproof material composition for hand-painting, wherein the ratio of the amino group amount (milli equivalent) of the aromatic polyamine to the plasticizer amount (g) is 0.6 or more and less than 1.6.   The urethane waterproof material composition for two-pack type hand-painting according to claim 1, wherein the NCO content of the main agent is 1.5 mass% or more and 3.3 mass% or less.   The urethane waterproof material composition for two-component hand-painting according to claim 1 or 2, wherein more than 70 equivalent% of the polyisocyanate is isophorone diisocyanate.   The urethane waterproof material composition for two-component hand-painting according to any one of claims 1 to 3, wherein more than 50 equivalent% of the main polyol is a polyoxyalkylene polyol.   The urethane waterproof material composition for two-pack type hand-painting according to any one of claims 1 to 4, wherein more than 50 equivalent% of the aromatic polyamine is diethyltoluenediamine.   At least one selected from the group consisting of organic stannic compounds, carboxylic acid metal salts, carboxylic acids, acid anhydrides and tertiary amines as accelerators in the main agent, curing agent or mixture of the main agent and the curing agent. The urethane waterproof material composition for two-pack type hand-painting according to any one of claims 1 to 5, wherein is formulated.   The curing agent according to any one of claims 1 to 6, wherein at least one selected from the group consisting of a carboxylic acid metal salt, a carboxylic acid and an acid anhydride is blended as a curing accelerator. Urethane waterproof material composition for liquid-type hand coating.   2 liquid of any one of Claims 1-6 by which at least 1 sort (s) selected from the group which consists of an organic stannic compound and a tertiary amine was mix | blended as a moisture hardening accelerator in the hardening | curing agent. Urethane waterproofing material composition for mold hand coating.   The main component isocyanate group-terminated prepolymer has an NCO content of more than 3.3% by mass and 4.5% by mass or less, and diethyltoluenediamine and 4,4′-methylenebis (N— The urethane waterproof material composition for two-component hand-painting according to any one of claims 1 to 8, comprising (sec-butylaniline) in an equivalent ratio of 51/49 to 97/3.   The two-component hand-painted urethane waterproofing according to any one of claims 1 to 9, after the primer layer is applied to the adherend, or after the primer layer and the waterproof layer are applied. A urethane waterproofing method including a step of applying a material composition.   The waterproof composition for two-component hand-painting according to any one of claims 1 to 9, after applying a ventilation buffer sheet, a polymer sheet, a root-proof sheet or a polymer coating material to an adherend. Urethane waterproofing method including the process of applying objects.