JP7436225B2 - Two-component room temperature curing urethane waterproof material composition for hand painting - Google Patents

Description

The present invention relates to a two-component, room-temperature-setting, hand-painted urethane waterproof material composition that can ensure a sufficient pot life throughout the year and has excellent durability.

Urethane waterproofing material is suitable for construction in irregularly shaped and narrow areas, so it can be used in balconies, balconies, open hallways of condominiums and other housing complexes, flat areas on relatively large rooftops, regardless of new construction or renovation work. Used on elevations, parapets, around pedestals, etc.

Typical urethane waterproofing materials are two-part liquid materials that are mixed using a stirrer and then applied by hand using a trowel, spatula, roller, brush, etc., and can be used for at least 30 minutes after being mixed using a stirrer. (hereinafter referred to as "pot life"). The pot life is generally defined as the time from when the two liquids are mixed at 23° C. until the viscosity reaches 60,000 mPa·s.
Hand-applied two-component room-temperature curing urethane waterproofing material has a summer formulation suitable for construction at temperatures above 30°C in the summer and one suitable for construction at temperatures below 5°C in the winter, since the outside temperature differs significantly between winter and summer construction. Generally, winter formulations suitable for construction are prepared, and waterproofing materials for flat areas are designed to have a pot life of 30 minutes or more at the construction temperature of each season (for this reason, For summer formulations, a pot life of at least 55 minutes at 23°C is required). In coating work, the longer the pot life is, the better, but generally speaking, trying to lengthen the pot life will result in poor curing properties, and the time it takes for a worker to get on the coating for the next process (hereinafter referred to as (referred to as the "possible construction time") will also become longer. In normal work, it is desirable to apply urethane waterproofing material in the evening and be ready for construction the next morning, and it is said that it is preferable that the construction time can be adjusted within about 17 hours throughout the year.

Traditionally, two-component, room-temperature-curing, hand-painted urethane waterproofing materials are based on an isocyanate-terminated prepolymer consisting of tolylene diisocyanate and polyoxypropylene polyol, and one of the curing agents contains active hydrogen, which has a relatively low reactivity. Polyoxypropylene polyol, which is a low-reactive secondary polyol, is mainly composed of 3,3'-dichloro-4,4'-diaminodiphenylmethane (hereinafter referred to as "MOCA"), which is a highly aromatic polyamine. It was common to use them together. Furthermore, lead carboxylate was used as a catalyst in order to accelerate the reaction of polyoxypropylene polyol, which has low reactivity. If lead carboxylate is not used, the reaction with the polyol will not be sufficiently promoted, so the reaction between the isocyanate group of the main ingredient and water will proceed, especially in summer, and as a result, the carbon dioxide gas produced as a by-product will cause foaming. This causes the physical properties to deteriorate.
The above waterproofing material is called MOCA crosslinked waterproofing material. MOCA is a raw material with high crystallinity and poor solubility, but it can be dissolved and stabilized to some extent in the polyoxypropylene polyol used as a hardening agent, making it a waterproof material with a pot life suitable for hand-coating. Therefore, it has been used as a general-purpose waterproofing material for a long time.

However, MOCA cross-linked waterproofing materials have had major environmental problems. MOCA used in the hardening agent is designated as a Class 2 Specified Chemical Substance under the Industrial Safety and Health Act, and since it is used in the hardening agent in an amount exceeding the upper limit of 1%, it may cause problems such as specified chemical substances. The product falls under the Preventive Regulations (hereinafter referred to as the "Specialized Regulations"). Furthermore, MOCA is classified as Group 1 (carcinogenic to humans) in carcinogenicity evaluation by IARC (International Agency for Research on Cancer).
Furthermore, the lead carboxylate compound that needs to be used as an accelerator is a material whose use is strictly restricted worldwide, and is designated as a Type 1 specified substance under the Chemical Substances Emission Control and Management Promotion Act (commonly known as the PRTR Act). It is designated as a chemical substance, and its use should be avoided from an environmental standpoint.

In recent years, similar to MOCA cross-linked waterproofing materials, the main ingredient is an isocyanate group-terminated prepolymer consisting of tolylene diisocyanate and polyoxypropylene polyol, and highly reactive aromatic compounds have been used instead of MOCA as active hydrogen compounds in the curing agent. A DETDA crosslinked urethane waterproofing material has been developed using diethyltoluenediamine (hereinafter referred to as "DETDA"), which is a polyamine. This method has good low-temperature curing properties due to the high reactivity of DETDA, but there is a major problem in securing a pot life in summer, and the curing agent is a polyol and an organic stannic urethanization catalyst. A method of using a compound or/and an imidazole compound having substituents at the 1st and 2nd positions (Patent Document 1), a method of using a mildly reactive aromatic secondary amine and a polyol together as a curing agent (Patent Document 2) A method has been proposed in which 20 equivalent % or more and 75 equivalent % or less of the polyol contained in the main ingredient is a diol, and a mildly reactive aromatic secondary amine is used in combination as a curing agent (Patent Document 3).

DETDA cross-linked waterproofing material does not use MOCA, a specific chemical substance, as a hardening agent, and there are no problems with curing or foaming properties even without the use of lead carboxylate, so it has become the mainstream instead of MOCA cross-linked waterproofing material. It is becoming.

Patent No. 5669813 Patent No. 6213954 Patent No. 6187964

When polyols and aromatic secondary amines are used in combination with DETDA crosslinked waterproofing materials to ensure pot life in the summer, durability such as heat resistance and alkali resistance is not necessarily sufficient. In recent years, it has become common for urethane waterproofing materials to be required to have a 10-year warranty, and it is necessary to emphasize not only initial performance but also durability. Regarding durability, the main deterioration factors are UV degradation and heat/alkali degradation, but UV degradation is usually protected by a top coat applied on top of the urethane waterproof layer, so it depends on the performance of the top coat. big. On the other hand, thermal/alkali deterioration depends on the performance of the urethane waterproof material composition itself, and is therefore very important in designing the urethane waterproof material. Regarding thermal deterioration test conditions, JIS A 6021 stipulates 80°C for one week, and for alkali deterioration test conditions, JIS A 6021 stipulates deterioration treatment at 23°C for one week, but a 10-year warranty is required. Nowadays, it has become a matter of course for products to be tested, and the current situation is to ensure practical performance by conducting evaluations under more severe deterioration test conditions.

In view of these problems, the present inventors conducted intensive studies on DETDA crosslinked waterproof materials, and found that a main ingredient containing an isocyanate group-terminated prepolymer consisting of tolylene diisocyanate and a polyol, an aromatic polyamine, and active hydrogen By using a curing agent containing polyalkanolamine as a reactive component, it has a two-component room temperature curing urethane waterproofing material composition that has sufficient pot life throughout the year and has excellent heat and alkali resistance. The inventors have discovered that a product can be obtained, and have completed the present invention.
The present invention is a two-component, room-temperature-curable, hand-painted urethane waterproof material composition comprising a main agent containing an isocyanate group-terminated prepolymer made of polyisocyanate and a polyol, and a curing agent containing an aromatic polyamine and a polyol as reactive components. The polyisocyanate includes tolylene diisocyanate, the aromatic polyamine includes diethyltoluenediamine, and the polyol in the curing agent includes a polyalkanolamine having three or more active hydrogens.

The present invention includes the following aspects.
[1] A two-component room-temperature-curable hand-painted urethane waterproof material composition consisting of a main agent containing an isocyanate group-terminated prepolymer composed of polyisocyanate and polyol, and a curing agent containing aromatic polyamine and polyol as reactive components. The polyisocyanate contains tolylene diisocyanate, the aromatic polyamine contains diethyltoluene diamine, and the polyol in the curing agent contains a polyalkanolamine having three or more active hydrogens. Urethane waterproof material composition.
[2] The polyalkanolamine having three or more active hydrogens includes triisopropanolamine, triethanolamine, 1-[bis(2-hydroxyethyl)amino)-2-propanol, diisopropanolamine, diethanolamine, N,N, At least one member selected from the group consisting of N',N'-tetrakis(2-hydroxypropyl)ethylenediamine and N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine, described in [1] A two-component, room-temperature-curing, hand-painted urethane waterproof material composition.
[3] The two-component room-temperature curing hand-painted urethane waterproofing material according to [1] or [2], which contains an organic tin compound or/and an imidazole compound having substituents at the 1st and 2nd positions as a urethanization catalyst. Composition.
[4] The equivalent ratio of aromatic polyamine to polyol in the curing agent is within the range of 40/60 to 90/10, and 40 equivalent% or more of the active hydrogen compounds contained in the curing agent are aromatic polyamines containing diethyltoluenediamine. The two-component room-temperature-curable hand-painted urethane waterproof material composition according to any one of [1] to [3], which is a polyamine and 5 equivalent % or more is a polyalkanolamine having three or more active hydrogen atoms. .
[5] The two-component room-temperature curing according to any one of [1] to [4], wherein more than 75 equivalent % of the polyol constituting the isocyanate group-terminated prepolymer consisting of polyisocyanate and polyol is diol. Urethane waterproof material composition for hand-painting.
[6] The two-component room-temperature-curable hand-painted urethane waterproof material composition according to any one of [1] to [5], wherein 70 equivalent % or more of the polyisocyanate is tolylene diisocyanate.

The two-component room-temperature curing hand-painted urethane waterproofing material of the present invention has a sufficient pot life throughout the year and is also excellent in durability such as heat resistance and alkali resistance.

The present invention relates to a two-component room-temperature curing urethane waterproof material composition for hand application. Here, the two liquids refer to the main agent and the curing agent. Room temperature curing type refers to a type that has the property of curing at outside temperature, that is, it is a type that is cured by being left in the surrounding natural environment without intentionally applying heat. Hand-applied means that it is applied by hand using a trowel, spatula, roller, brush, etc.
The two-component room-temperature curable hand-painted urethane waterproof material composition of the present invention is composed of a base agent containing an isocyanate group-terminated prepolymer consisting of tolylene diisocyanate and a polyol, and a curing agent containing an aromatic polyamine and a polyol as reactive components. The aromatic polyamine in the curing agent contains diethyltoluenediamine, and the polyol in the curing agent contains a polyalkanolamine having three or more active hydrogen atoms.

(Base polyisocyanate)
The base material contains an isocyanate group-terminated prepolymer consisting of polyisocyanate and polyol. The present invention needs to contain tolylene diisocyanate as the polyisocyanate, and preferably 70 equivalents or more of the polyisocyanate is tolylene diisocyanate, more preferably 80 equivalents or more, and 90 equivalents. % or more is most preferable. As tolylene diisocyanate, one having a 2,4-isomer content of 65 to 100% by mass can be used. Specifically, commercially available T-100 (approximately 100% by mass of the 2,4-isomer), T-80 (approximately 80% by mass of the 2,4-isomer), and T-65 (approximately 80% by mass of the 2,4-isomer) (approximately 65% by mass) or a mixture thereof.

Incidentally, some other polyisocyanates may also be used in combination. Isocyanates that can be used in combination include aliphatic or alicyclic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated xylylene diisocyanate. group polyisocyanates, aromatic polyisocyanates such as xylylene diisocyanate, tetramethylxylylene diisocyanate, and diphenylmethane diisocyanate, and their derivatives such as dimers, allophanates, biurets, adducts, and isocyanurates. and mixtures thereof can also be used in part.

(Main polyol)
As the polyol used as the main ingredient, polyols that are normally used as the main ingredient of urethane waterproofing materials can be used, but in order to use a main ingredient with low viscosity and good workability, it is necessary to use polyoxypropylene polyol or polyol with a molecular weight of 300 to 8000. It is preferable to use a polyether polyol such as oxyethylene polyoxypropylene polyol. Further, other high molecular weight polyols such as polyester-based polyols can also be used as long as they are in part.
Furthermore, short chain polyols such as 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, propylene glycol, dipropylene glycol can also be used.

Regarding the number of functional groups in the polyol used as the main ingredient, when polyols or aromatic secondary amines are used together as a curing agent, heat resistance and alkali resistance tend to decrease. It was necessary to increase the number of branch points by using a larger amount of polyol than the basic group. However, in the present invention, since a polyalkanolamine having three or more active hydrogen atoms is used as a curing agent, heat resistance and alkali resistance are significantly improved. As a result, it is no longer necessary to use a large amount of polyol having three or more functional groups in the main ingredient, and it has become possible to use a large amount of diol, which is advantageous in securing a pot life. Therefore, in the polyol used as the main ingredient, it is preferable to use more than 75 equivalent % of diol and 25 equivalent % or less of triol or more, and more preferably to use 80 equivalent % or more of diol and 20 equivalent % or less of triol or more. If the diol content is 75 equivalent % or less, it becomes difficult to ensure a sufficient pot life. Although the upper limit of the proportion of diol is not limited, preferably less than 95 equivalent % of diol is used, and more than 5 equivalent % of triol is used.

(Base NCO content)
In general, in order to ensure pot life, it is effective to reduce the NCO content of the base material, but as a result, curing properties may decrease, and the strength and heat resistance required for urethane waterproofing materials may decrease. - A problem arises in that durability such as alkali resistance decreases.
However, since the urethane waterproof material composition of the present invention contains diethyltoluenediamine and a polyalkanolamine having three or more active hydrogen atoms as a curing agent, it is necessary for urethane waterproof materials even in areas where the NCO content is relatively low. The strength and durability can be ensured. In the present invention, by setting the NCO content of the base agent in the range of 1.5 to 3.5% by mass, the strength and durability required for urethane waterproofing materials are ensured while having sufficient pot life. This is preferable because it can be done. In addition, from the viewpoint of securing pot life and workable time, it is more preferable that the NCO content is 1.7 to 3.3% by mass, and more preferably 1.9 to 3.1% by mass. Most preferred. If the NCO content is less than 1.5% by mass, it will be difficult to ensure the strength and durability required for the urethane waterproofing material, and if it exceeds 3.5% by mass, it will be difficult to ensure a usable life.

(Base NCO group/OH group equivalent ratio)
The NCO group/OH group equivalent ratio, which is the ratio of the isocyanate group to the OH group of the polyol during the production of the main ingredient used in the present invention, is preferably in the range of 1.5 to 2.5, and 1.6 or more. It is more preferably less than 2.3, and most preferably 1.7 or more and less than 2.1.
Note that when the NCO group/OH group equivalent ratio is less than 1.5, the viscosity of the base agent increases significantly, and when it exceeds 2.5, it becomes difficult to reduce the amount of free TDI in the base agent to 1% by mass or less, resulting in poor occupational safety and health. This is not desirable because it increases the possibility that it will be treated as a specified chemical substance under the law.

(Synthesis of main agent)
The isocyanate group-terminated prepolymer of the present invention can be synthesized by heating and mixing a polyisocyanate containing tolylene diisocyanate and a polyol at 60 to 120°C for about 2 to 12 hours. In addition, if the reaction is slow, a general urethanization reaction accelerator can be used as necessary.

(Active hydrogen compound in curing agent)
The curing agent of the present invention contains an aromatic polyamine and a polyol as active hydrogen compounds. Aromatic polyamines include diethyltoluenediamine (DETDA). DETDA has isomers such as 3,5-diethyl-2,4-toluenediamine and 3,5-diethyl-2,6-toluenediamine, but any isomer may be used, and they A mixture of these may also be used. For industrial use, for example, Ettacure 100 (mass ratio of 2,4-isomer/2,6-isomer 80/20) manufactured by Albemarle is available.

Moreover, it is preferable that 40 equivalent % or more of the active hydrogen compound in the curing agent is DETDA, more preferably 45 equivalent % or more, and most preferably 50 equivalent % or more. Unless DETDA, which is highly cohesive, highly reactive, and liquid and has good solubility, is 40 equivalent % or more, it is difficult to obtain a waterproof material with good curability and high physical properties.
Although it is preferred that all of the aromatic polyamines in the curing agent be DETDA, the curing agent can include aromatic polyamines other than DETDA. When the curing agent contains an aromatic polyamine other than DETDA, DETDA is preferably 50 equivalent % or more, more preferably 60 equivalent % or more, and 70 equivalent % or more of the total amount of aromatic polyamines. is even more preferable.

An aromatic polyamine that can be used in combination with DETDA is Curehard (registered trademark) MED (4,4'-methylenebis(2-ethyl-6-methylaniline) manufactured by Kumiai Chemical Industry Co., Ltd., which has the same high reactivity as DETDA. ), Kayahard (registered trademark) AA (4,4'-methylenebis(2-ethylaniline)) manufactured by Nippon Kayaku Co., Ltd., Kayabond (registered trademark) C-300 (4,4' manufactured by Nippon Kayaku Co., Ltd.) -methylenebis(2,6-diethylaniline)), Kayabond (registered trademark) C-400 (4,4'-methylenebis(2,6-diiso-propylaniline)) manufactured by Nippon Kayaku Co., Ltd. .

In addition, low-reactivity aromatic polyamines such as Albemarle's Etacure 420 (4,4'-methylenebis(N-sec-butylaniline)), Albemarle's Etacure 300 (dimethylthiotoluenediamine), and Kumiai Chemical Co., Ltd. Elasmer (registered trademark) 650P (polytetramethylene glycol bis(p-aminobenzoate)) manufactured by Co., Ltd., Porea (registered trademark) SL-100A (poly(tetramethylene/3-methyltetramethylene ether) manufactured by Kumiai Chemical Co., Ltd. ) glycol bis(4-aminobenzoate)) and the like can also be used. Among them, Etacure 420 is not as highly cohesive as DETDA, but it has low reactivity, which has the effect of extending pot life, and it does not significantly worsen curing properties, so it is particularly preferred to use. Can be done.

The curing agent of the present invention contains an aromatic polyamine and a polyol as active hydrogen compounds. Polyols include polyalkanolamines having three or more active hydrogens. Here, active hydrogen specifically refers to active hydrogen consisting of a hydroxyl group and an amino group. Examples of polyalkanolamines having three or more active hydrogens include N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, N,N,N',N'-tetrakis(2-hydroxyethyl) Tetraalkanol diamines having 4 hydroxyl groups such as ethylenediamine, triisopropanolamine, triethanolamine, trialkanolamines having 3 hydroxyl groups such as 1-[bis(2-hydroxyethyl)amino)-2-propanol, diisopropanolamine Dialkanolamines having two hydroxyl groups and one amino group, such as diethanolamine, can be used. Among them, triisopropanolamine, triethanolamine, diisopropanolamine, and diethanolamine are preferred, and triisopropanolamine is particularly preferably used.

Further, it is preferable that 5 equivalent % or more of the active hydrogen compound in the curing agent is a polyalkanolamine having 3 or more active hydrogens, more preferably 10 equivalent % or more, and 15 equivalent % or more. Most preferred. If the polyalkanolamine having three or more active hydrogen atoms is less than 5 equivalent %, it is difficult to obtain a waterproof material with sufficient durability such as heat resistance and alkali resistance of the coating film.
All of the polyols in the curing agent are preferably polyalkanolamines having three or more active hydrogens, but the curing agent can contain polyols other than polyalkanolamines having three or more active hydrogens. When the curing agent contains a polyol other than polyalkanolamine having three or more active hydrogens, the polyalkanolamine having three or more active hydrogens preferably accounts for 20 equivalent% or more of the total amount of polyols in the curing agent, and 25 It is more preferably at least 30 equivalent %, even more preferably at least 30 equivalent %.

Note that polyols that can be used in combination with polyalkanolamines having three or more active hydrogens include polyether polyols, polyester polyols, alkyl polyols, and the like. Among them, polyester polyols are preferred, and polyols mainly composed of diols having side chains such as MPD (3-methyl-1,5-pentanediol) and MOD (2-methyl-1,8-octanediol) and succinic acid. Polyester with low crystallinity and good hydrolysis resistance obtained by reaction with aliphatic or alicyclic dicarboxylic acids such as , adipic acid, azelaic acid, sebacic acid, tetrahydrophthalic acid, hexahydrophthalic acid, etc. Polyols are more preferred. Furthermore, low-crystalline aromatic polyester polyols obtained by reacting diols with side chains such as MPD and MOD with aromatic dicarboxylic acids such as phthalic acid and phthalic anhydride have excellent hydrolysis resistance and mechanical strength. Therefore, it is the most preferred. Specific examples include Kuraray Polyol P-520 (number average molecular weight 500) and Kuraray Polyol P-530 (number average molecular weight 500) manufactured by Kuraray Co., Ltd.

On the other hand, the equivalent ratio of aromatic polyamine/polyol in the curing agent is preferably in the range of 40/60 to 90/10, more preferably in the range of 45/55 to 80/20.

(Base isocyanate/curing agent active hydrogen equivalent ratio)
The equivalent ratio of total isocyanate groups in the base resin to active hydrogen (amino groups + hydroxyl groups) in the curing agent is preferably in the range of 0.8 to 1.6, preferably 0.9 to 1.5. More preferably, it is 0.95 to 1.4. If the base resin isocyanate group/curing agent active hydrogen equivalent ratio is less than 0.8, the active hydrogen will be in excess, resulting in insufficient increase in the molecular weight of the cured product and poor physical properties; if it exceeds 1.6, strength and durability will deteriorate. It becomes insufficient and the curability also decreases.

(hardening accelerator)
In the present invention, since the curing agent contains DETDA, which is highly reactive with isocyanate groups, as an aromatic polyamine, there is no need to use a curing accelerator, but fast curing is required. Formulas for use in the winter season when the setting and construction temperature is low, formulations in which a large amount of polyol is used in the curing agent, or cases where the equivalent ratio of base isocyanate to curing agent active hydrogen is high and it is necessary to accelerate the reaction between excess isocyanate groups and moisture. In such cases, a curing accelerator can be used as necessary.

In the present invention, common curing accelerators for polyurethane such as organic acids, organic acid metal salts, acid anhydrides, organic stannic compounds, and tertiary amine compounds can be used. Among these, organic stannic compound catalysts are preferred because they can improve curability without shortening pot life. The organic stannic compound catalyst can be added to the main agent in advance, but since there is a risk of impairing the storage stability of the main agent, it is preferable to incorporate it into the curing agent. It is preferable to add less than 0.03% by mass. If more than 0.03% by mass is added, the reaction with water will be promoted too much, making the coating film more likely to foam and at the same time, the heat resistance will decrease. If less than 0.0005% by mass, the catalyst will The effect is insufficient.

Specific examples of organic stannic compounds include dibutyltin oxide, dioctyltin oxide, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin di2-ethylhexanoate, dioctyltin diacetate, dioctyltin dilaurate, dibutyltin dimercaptide, Examples include dibutyltin bisacetylacetonate, dibutyltin oxylaurate, dioctyltin dineodecanate, dibutyltin bisbutyl maleate, dioctyltin 2-ethylhexyl maleate, and in particular, dibutyltin dilaurate, dioctyltin dilaurate, and dibutyltin dimercaptide. preferable.

In winter formulations, it is preferred to use a tertiary amine catalyst. Among the tertiary amine catalysts, imidazole compounds are preferred and can provide a non-foaming coating film with good low temperature curability. Among them, imidazole catalysts, which have substituents at the 1st and 2nd positions, promote the reaction with DETDA, polyol, and moisture (moisture) in a well-balanced manner even at low temperatures, and produce coatings with high strength and high heat resistance even in winter. is a more preferred catalyst that can be provided. Imidazole catalysts having substituents at the 1st and 2nd positions can also be used in combination with organometallic catalysts, and among them, it is preferable to use them in combination with organic stannic compound catalysts. We can provide waterproofing materials with good hardening properties, high physical properties, and high heat resistance.

Further, although imidazole catalysts having substituents at the 1st and 2nd positions tend to shorten the pot life, they can also be blended as a catalyst for curing adjustment throughout the year. Furthermore, it can be added at the construction site and used as an on-site addition type curing accelerator throughout the year. Examples of imidazole catalysts having substituents at the 1- and 2-positions include 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-benzyl-2-methylimidazole, and 1-benzyl-2- Examples include phenylimidazole, 1,2-dimethylimidazole and 1-isobutyl-2-methylimidazole are preferred, and 1-isobutyl-2-methylimidazole is more preferred because it is liquid at room temperature and is easy to handle.

In addition, the curing agent can contain plasticizers, fillers, antifoaming agents, wetting agents, weatherability imparting agents, etc. that are normally used in urethane waterproofing materials, and thixotropic agents such as colloidal calcium carbonate can be added to the curing agent. By blending, it is also possible to create a urethane waterproofing material that can be applied to vertical surfaces.

(Plasticizer)
As the plasticizer used in the present invention, a plasticizer that can be generally blended into urethane resins can be used. Specific examples include phthalic acid esters such as diisononyl phthalate (DINP), dioctyl phthalate (DOP), and butylbenzyl phthalate (BBP), aliphatic dibasic acid esters, phosphoric acid esters, trimellitic acid esters, and sebacic acid. Examples include 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 higher, are preferably used because they do not easily lose mass over a long period of time and are aromatic polyesters and do not easily undergo hydrolysis. can. It is also possible to use a solvent in the hardening agent, but there is a risk of shrinkage due to volatilization after construction, a tendency for the inorganic filler to settle, and there are environmental problems, so it should not exceed 5% by mass. It is preferable to use it, and it is more preferable not to use it.

In the present invention, the amount of plasticizer used is preferably 15 to 90 parts by weight, and 20 to 80 parts by weight, based on 100 parts by weight of the prepolymer component in the base resin, from the viewpoint of ensuring pot life and physical properties. It is more preferable. If the amount of plasticizer is less than 15 parts by mass, it is difficult to obtain an economical urethane waterproofing material with sufficient pot life, while if it exceeds 90 parts by mass, it will not be possible to ensure the strength and durability required for a urethane waterproofing material. This makes it difficult to do so, and the bleed-out of plasticizer becomes severe. In principle, the plasticizer is blended with the curing agent, but a portion of the plasticizer can also be blended with the base resin.

(Inorganic filler)
Further, in the present invention, an inorganic filler can be added to the curing agent. By incorporating an inorganic filler, it is possible to create a versatile waterproofing material that is highly economical. Calcium carbonate is preferred as the inorganic filler. Calcium carbonate has a high economical effect, and at the same time has good dispersibility when producing a hardener, has little viscosity even when mixed in large amounts, and can easily reduce sedimentation when storing the hardener. It also has a high reinforcing effect. Note that there are various types of calcium carbonate such as heavy calcium carbonate, light calcium carbonate, and surface-treated colloidal calcium carbonate, and any calcium carbonate can be used.

Further, inorganic fillers such as silica, kaolin, talc, bentonite, aluminum hydroxide, and barium hydroxide can be used in part. Incidentally, the above-mentioned inorganic fillers contain adhering water, and although this adhering water is thought to gradually react with the isocyanate group, the adhering water is generally not considered to be active hydrogen. Additionally, it is generally believed that the moisture (moisture) that is involved when mixing the base agent and curing agent, and the moisture (moisture) that is absorbed from the coating surface after applying the waterproofing material, reacts with the isocyanate group to some extent. It is.

In the present invention, by blending a relatively large amount of plasticizer on the curing agent side, a large amount of inorganic filler can also be blended, thereby making it possible to achieve a 1/2 (mass ratio) blending ratio of main agent/curing agent. Therefore, it can be made into a versatile waterproofing material with excellent economic efficiency, and it can be made into a waterproofing material that satisfies the strength and durability required for urethane waterproofing materials while ensuring a pot life. can. The inorganic filler is preferably blended in an amount of 20 to 80% by mass based on the total amount of the curing agent. If it is less than 20% by mass, the reinforcing effect will be insufficient and economic efficiency will be impaired, and if it exceeds 80% by mass, thickening will increase and workability will deteriorate.

(Other additives)
In addition, appropriate amounts of additives such as wetting agents, antifoaming agents, pigments, and weatherability imparting agents may be added to the curing agent as necessary.

(Base agent/curing agent blending ratio)
The blending ratio of the main ingredient and the curing agent is not particularly limited, but the mass ratio is preferably in the range of 1/1 to 1/3, more preferably 1/1 to 1/2.

(Waterproofing method)
Further, the two-component room-temperature curing hand-painted urethane waterproofing material of the present invention cannot be applied directly to an inorganic base such as concrete. In the case of an inorganic base, it does not adhere to the urethane waterproofing material, so it can be applied after applying a primer that can block moisture from the base to some extent and ensure adhesion. Additionally, in some cases, an intermediary primer can be applied over the existing urethane waterproof layer, including during renovations. Furthermore, it can be applied to an inorganic base by fixing a breathable buffer sheet, a polymeric sheet such as a PVC sheet, a rubber sheet, or a nonwoven fabric sheet using a primer, adhesive, mechanical fixing, laying, etc. Furthermore, even in the case of a metal base, adhesion cannot be ensured even if the urethane waterproofing material of the present invention is directly applied, so it can be applied after applying a dedicated primer.
The present invention is not intended to repair asphalt-based waterproof layers, but rather to waterproof and protect inorganic bases such as concrete, metal bases, polymeric resin bases, and rubber bases. Furthermore, when the two-component room-temperature curing type hand-painted urethane waterproofing material of the present invention is used in areas exposed to direct sunlight, it is a general rule to apply a top coat.

In the present invention, in consideration of practical durability, durability was evaluated under test conditions stricter than the deterioration treatment conditions specified in JIS A 6021. Specifically, according to JIS A 6021, heat treatment is performed at 80°C for 4 weeks (JIS A 6021: 1 week), and alkali treatment is performed at 60°C (JIS A 6021: 23°C) for 1 week. Deterioration treatment was carried out. A highly durable waterproof material that fully guarantees a 10-year guarantee must have a tensile strength ratio of 90% or more after heat treatment under the above conditions, an elongation rate at break of 400% or more, and a tensile strength after alkali treatment. It is preferable that the ratio is 80% or more, the elongation at break is 400% or more, the tensile strength ratio after heat treatment is 95% or more, the elongation at break is 400% or more, and the tensile strength after alkali treatment is It is more preferable that the thickness ratio is 85% or more and the elongation at break is 400% or more.

[raw materials]
The raw materials used in the following Examples and Comparative Examples are as follows.
Coronate T-80: 2,4-tolylene diisocyanate/2,6-tolylene diisocyanate = 80/20 (mass ratio) mixture, NCO content 48.3% by mass, manufactured by Tosoh Corporation SUNIX PP- 2000: Polyoxypropylene diol, average molecular weight 2000, OH value 56.1 mgKOH/g, Sanyo Chemical Industries, Ltd. SANNIX GA-3000: Polyoxypropylene triol, average molecular weight 3000, OH value: 56.1 mgKOH/g, Sanyo Chemical Industry Co., Ltd. MC-2000 Solvent: Petroleum-based hydrocarbon solvent, normal paraffin, isoparaffin mixture, Sankyo Chemical Co., Ltd. DETDA: Etacure 100, diethyltoluenediamine, 2,4-diamino-3,5-diethyltoluene/ Mixture of 2,6-diamino-3,5-diethyltoluene = 80/20 (mass ratio), Albemarle Etacure 420: 4,4'-methylenebis(N-sec-butylaniline), aromatic secondary diamine, Kuraray Polyol P-530, manufactured by Albemarle Co., Ltd.: Aromatic polyester diol obtained by the reaction of 3-methyl-1,5-pentanediol and isophthalic acid, average molecular weight 500, OH value: 224.4 mgKOH/g, Kuraray Co., Ltd. Manufactured by Triisopropanolamine: Reagent, manufactured by Tokyo Chemical Industry Co., Ltd. Diisopropanolamine: Reagent, manufactured by Tokyo Chemical Industry Co., Ltd. DINP: Sansocizer DINP, diisononyl phthalate, manufactured by Shin Nippon Chemical Co., Ltd. Dioctyltin dilaurate: KS-1200A-1, Kyodo Yakuhin Co., Ltd. NC-IM: 1-isobutyl-2-methylimidazole, Air Products Japan Co., Ltd. Additives: Kusumoto Kasei Co., Ltd. Calcium carbonate: NS#100, Nitto Funka Kogyo Co., Ltd.

[Preparation of main ingredient]
According to the formulations in Tables 1 to 4, polyol and solvent were charged into a four-necked flask, and then TDI was charged. Thereafter, the mixture was reacted at 105 to 110° C. for 4 to 8 hours with stirring to obtain a main ingredient.

[Preparation of curing agent]
According to the formulations in Tables 1 to 4, liquids were charged into a polypropylene container, mixed at low speed with a stirrer (dissolver blade) to make it uniform, and then calcium carbonate was added and mixed at 1500 rpm for 10 minutes to obtain a curing agent.

[Example 1, 2]
In Examples 1 and 2, the base resin and curing agent were obtained according to the formulations shown in Table 1. A urethane waterproof material composition was obtained by mixing these main ingredients and curing agent at a mass ratio of 1:2.
The diol/triol equivalent ratio of the main ingredient is 85/15, DETDA is used as the aromatic polyamine as the curing agent, and triisopropanolamine is used as the polyol, and the equivalent ratio of the aromatic polyamine and polyol is 55/45 and 60/40, respectively. In Examples 1 and 2, the pot life at 23°C is 72 minutes and 61 minutes, respectively, which is long enough for a summer formulation, and the workable time at 23°C is within 15 hours, so it can be applied the next day. there were. Furthermore, all of the obtained coating films exhibited good initial physical properties and sufficiently high heat and alkali resistance as highly elongated hand-coated urethane waterproofing materials.

[Examples 3 and 4]
In Examples 3 and 4, the base resin and curing agent were obtained according to the formulations shown in Table 1. A urethane waterproof material composition was obtained by mixing these main ingredients and curing agent at a mass ratio of 1:2.
The diol/triol equivalent ratio of the main ingredient was 85/15, DETDA and Etacure 420 were used together as aromatic polyamines as the curing agent, triisopropanolamine was used as the polyol, and the equivalent ratio of aromatic polyamine and polyol was 70/30 and 75, respectively. /25 Examples 3 and 4 have a pot life of 63 minutes and 65 minutes, respectively, at 23°C, which is long enough as a summer formulation, and the workable time at 23°C is within 15 hours, so it can be used the next day. Construction was possible. Furthermore, all of the obtained coating films exhibited good initial physical properties and sufficiently high heat and alkali resistance as highly elongated hand-coated urethane waterproofing materials.

[Example 5]
In Example 5, a base material and a curing agent were obtained according to the formulation shown in Table 1. A urethane waterproof material composition was obtained by mixing these main ingredients and curing agent at a mass ratio of 1:2.
The diol/triol equivalent ratio of the main ingredient was 85/15, DETDA and Etacure 420 were used together as aromatic polyamines as the curing agent, triisopropanolamine and Kuraray Polyol P-530 were used together as polyols, and the equivalent ratio of aromatic polyamine and polyol was Example 5, which has a ratio of 70/30, has a pot life of 67 minutes at 23°C, which is long enough for a summer formulation, and the workable time at 23°C is within 15 hours, so it can be applied the next day. there were. Furthermore, the obtained coating film showed good initial physical properties and sufficiently high heat and alkali resistance as a highly elongated hand-coated urethane waterproofing material.

[Example 6]
In Example 6, a base material and a curing agent were obtained according to the formulation shown in Table 2. A urethane waterproof material composition was obtained by mixing these main ingredients and curing agent at a mass ratio of 1:2.
The diol/triol equivalent ratio of the main ingredient is 80/20, DETDA and Etacure 420 are used together as aromatic polyamines as the curing agent, triisopropanolamine is used as the polyol, and the equivalent ratio of aromatic polyamine and polyol is 75/25. In Example 6, the pot life at 23° C. was 70 minutes, which is long enough for a summer formulation, and the workable time at 23° C. was within 15 hours, so it could be applied the next day. Furthermore, the obtained coating film showed good initial physical properties and sufficiently high heat and alkali resistance as a highly elongated hand-coated urethane waterproofing material.

[Examples 7 to 10]
In Examples 7 to 10, main ingredients and curing agents were obtained according to the formulations shown in Table 2. A urethane waterproof material composition was obtained by mixing these main ingredients and curing agent at a mass ratio of 1:2.
The diol/triol equivalent ratios of the main ingredients were 80/20, 90/10, 95/5, and 100/0, respectively, DETDA was used as the aromatic polyamine as the curing agent, triisopropanolamine was used as the polyol, and the equivalents of the aromatic polyamine and the polyol were used. Examples 7 to 10 with ratios of 55/45, 65/35, 70/30, and 75/25 have pot lifes of 64 minutes, 58 minutes, 64 minutes, and 57 minutes at 23°C, respectively, which are suitable for summer use. The formulation was sufficiently long, and the workable time at 23°C was within 15 hours in all cases, making it possible to work the next day. Furthermore, all of the obtained coating films exhibited good initial physical properties and sufficiently high heat and alkali resistance as highly elongated hand-coated urethane waterproofing materials.

[Example 11, 12]
In Examples 11 and 12, a base material and a curing agent were obtained according to the formulations shown in Table 3. A urethane waterproof material composition was obtained by mixing these main ingredients and curing agent at a mass ratio of 1:2.
The same procedure as in Example 6 was carried out except that triethanolamine or diisopropanolamine was used as the curing agent polyol instead of triisopropanolamine. In Examples 11 and 12, the pot life at 23°C was 55 minutes and 68 minutes, respectively, which is long enough for a summer formulation, and the workable time at 23°C was within 15 hours, so it could be applied the next day. . Furthermore, all of the obtained coating films exhibited good initial physical properties and sufficiently high heat and alkali resistance as highly elongated hand-coated urethane waterproofing materials.

[Example 13]
In Example 13, a main ingredient and a curing agent were obtained according to the formulation shown in Table 3. A urethane waterproof material composition was obtained by mixing these main ingredients and curing agent at a mass ratio of 1:2.
The same procedure as in Example 6 was conducted except that 0.06% by mass of NC-IM was added as a urethanization catalyst to the curing agent. In Example 13, the pot life at 23° C. was 44 minutes, which is sufficiently long as a winter formulation, and the workable time at 23° C. was 8 hours, so it could be applied the next day. Furthermore, the obtained coating film showed good initial physical properties and sufficiently high heat and alkali resistance as a highly elongated hand-coated urethane waterproofing material.

[Comparative example 1]
In Comparative Example 1, a base material and a curing agent were obtained according to the formulation shown in Table 4. A urethane waterproof material composition was obtained by mixing these main ingredients and curing agent at a mass ratio of 1:2.
Example 1 was carried out in the same manner as in Example 1, except that only DETDA was used as the curing agent active hydrogen without using a polyalkanolamine having three or more active hydrogens. In Comparative Example 1, the pot life at 23° C. was as short as 32 minutes, and it was thought that problems would arise in workability during high temperatures such as summer.

[Comparative example 2]
In Comparative Example 2, a base material and a curing agent were obtained according to the formulation shown in Table 4. A urethane waterproof material composition was obtained by mixing these main ingredients and curing agent at a mass ratio of 1:2.
Example 1 except that only Kuraray Polyol P-530 and DETDA were used as the curing agent active hydrogen without using a polyalkanolamine having three or more active hydrogens, and the equivalent ratio of aromatic polyamine and polyol was 60/40. I did the same thing. Comparative Example 2 had a pot life of 63 minutes at 23°C, which is long enough for a summer formulation, but the workable time at 23°C was 18 hours, and it could not be applied the next day. Furthermore, the obtained coating film showed good initial physical properties as a highly elongated hand-coated urethane waterproofing material, but the tensile strength ratio after heat treatment and alkali treatment was 89% and 79%, respectively. It was lower than Examples 1 to 13 in which polyalkanolamines having three or more hydrogen atoms were used, and was insufficient as a highly durable waterproof material.

[Comparative example 3]
In Comparative Example 3, a base material and a curing agent were obtained according to the formulation shown in Table 4. A urethane waterproof material composition was obtained by mixing these main ingredients and curing agent at a mass ratio of 1:2.
Same as Example 1 except that polyalkanolamine having three or more active hydrogens was not used as the curing agent active hydrogen, DETDA and Etacure 420 were used together, and the equivalent ratio of aromatic polyamine and polyol was 100/0. went. Comparative Example 3 had a pot life of 79 minutes at 23°C, which is long enough for a summer formulation, and the workable time at 23°C was within 15 hours, allowing it to be applied the next day. Furthermore, the obtained coating film showed good initial physical properties as a highly elongated hand-coated urethane waterproofing material, but the tensile strength ratio after heat treatment and alkali treatment was 71% and 52%, respectively. It was lower than Examples 1 to 13 in which polyalkanolamines having three or more hydrogen atoms were used, and was insufficient as a highly durable waterproof material.

[Comparative example 4]
In Comparative Example 4, a base material and a curing agent were obtained according to the formulation shown in Table 4. A urethane waterproof material composition was obtained by mixing these main ingredients and curing agent at a mass ratio of 1:2.
A polyalkanolamine having three or more active hydrogens is not used as the curing agent active hydrogen, DETDA and Etacure 420 are used together as the aromatic polyamine as the curing agent, and Kuraray Polyol P-530 is used as the polyol. The same procedure as in Example 1 was carried out except that the equivalent ratio of polyol was 75/25. In Comparative Example 4, the pot life at 23°C was 66 minutes, which is long enough for a summer formulation, and the workable time at 23°C was within 15 hours, so it could be applied the next day. Furthermore, the obtained coating film showed good initial physical properties as a highly elongated hand-coated urethane waterproofing material, but the tensile strength ratio after heat treatment and alkali treatment was 86% and 71%, respectively. It was lower than Examples 1 to 13 in which polyalkanolamines having three or more hydrogen atoms were used, and was insufficient as a highly durable waterproof material.

The measurement method for each evaluation item is as follows.

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

[Free TDI (mass%)]
Approximately 10 g of the base ingredient is accurately weighed into an eggplant-shaped flask, 100 mL of isoamylbenzoic acid is added and dissolved, and the mixture is distilled using a rotary evaporator (isoamylbenzoic acid and TDI are azeotroped). When evaporation has stopped, 50 mL of isoamylbenzoic acid is added and further distilled. Add 10 mL of 0.5N di-n-butylamine (toluene solution) and an appropriate amount of bromophenol blue to the recovered distillate, and then add about 300 mL of methanol. This mixture is titrated with 0.25N hydrochloric acid solution. Free TDI is determined by the following formula.
Free TDI (mass%) = [(Blank titration value - Titration value of recovered distillate) x Factor of 0.25N hydrochloric acid solution x 0.25 ÷ (Main ingredient weight x Equivalent per 1 g of TDI)] x 100

[Pot life (minutes)]
In an air-circulating environmental test chamber at 23°C and 50% humidity, the time from the time when the base agent and curing agent are mixed at a predetermined ratio and stirring is started until the viscosity at 2 rpm reaches 60,000 mPa・s using a BH type viscometer. It was measured. (Summer formulations are recommended for 55 minutes or more)

[Workable time (hardening)]
In an air-circulating environmental test chamber at 23°C or 5°C and 50% humidity, 2 kg/m ² of waterproofing material made by stirring and mixing the base agent and hardening agent at a predetermined ratio was applied, although it was not completely cured. The time from when it was possible to walk on the paint film with shoes to when the next process could be started was measured. (Construction can be done the next day within 17 hours.)

[Tensile strength (N/mm ² )]
Test pieces were cured at 23°C and 50% humidity for 7 days, and measurements were taken based on JIS A 6021. ² or more).

[Elongation rate at break (%)]
Test specimens were cured at 23°C and 50% humidity for 7 days, and measurements were taken based on JIS A 6021. ).

[Tear strength (N/mm)]
Test specimens were cured at 23°C and 50% humidity for 7 days, and measurements were taken based on JIS A 6021 (JIS A 6021 urethane rubber high elongation type has a tear strength standard of 14 N/mm or more). .

[Tensile strength ratio after heat treatment (%) and elongation at break (%) (heat resistance)]
After curing for 7 days at 23°C and 50% humidity, test pieces were heat-treated by placing them in a dryer at 80°C for 28 days (7 days at 80°C according to JIS A 6021). The tensile strength ratio of Tensile strength ratio at 80°C for 7 days: 80% or more, elongation at break: 400% or more).

[Tensile strength ratio (%) after alkali treatment (alkali resistance)]
After curing at 23°C and 50% humidity for 7 days, the tensile strength compared to before treatment was carried out according to JIS A 6021, except that the alkali treatment conditions were changed to 60°C and 7 days (JIS A 6021: 23°C and 7 days). The strength ratio and elongation rate at break were measured, and a tensile strength ratio of 80% or more and elongation rate at break of 400% or more was considered high durability (JIS A 6021 urethane rubber high elongation type standard: 23°C , tensile strength ratio at 7 days of 60% or more, elongation at break of 400% or more).

The two-component room-temperature curing hand-painted urethane waterproofing material composition of the present invention can be suitably used as a highly durable waterproofing material for waterproofing layers on rooftops of buildings, balconies of housing complexes such as condominiums, and the like.

Claims (5)

A two-component room-temperature-curable hand-painted urethane waterproof material composition comprising a main agent containing an isocyanate group-terminated prepolymer consisting of polyisocyanate and polyol, and a curing agent containing aromatic polyamine and polyol as reactive components, The polyisocyanate contains tolylene diisocyanate, the aromatic polyamine contains diethyltoluenediamine, the polyol in the curing agent contains a polyalkanolamine having 3 or more active hydrogens, and the polyalkanol having 3 or more active hydrogens. A two-liquid room temperature curing type in which the amine is at least one selected from the group consisting of triisopropanolamine, triethanolamine, 1-[bis(2-hydroxyethyl)amino)-2-propanol, diisopropanolamine and diethanolamine. Hand-painted urethane waterproof material composition. 2. The two-component room-temperature curable hand-painted urethane waterproof material composition according to claim 1 , which contains an organic tin compound and/or an imidazole compound having substituents at the 1st and 2nd positions as a urethanization catalyst. The equivalent ratio of aromatic polyamine and polyol in the curing agent is within the range of 40/60 to 90/10, and 40 equivalent% or more of the active hydrogen compound contained in the curing agent is diethyltoluenediamine, and 5 equivalent% or more The two-component room-temperature-curable hand-painted urethane waterproof material composition according to claim 1 or 2 , wherein is a polyalkanolamine having three or more active hydrogen atoms. The two-component room-temperature-curing hand-coated urethane according to any one of claims 1 to 3 , wherein more than 75 equivalent percent of the polyol constituting the isocyanate group-terminated prepolymer consisting of a polyisocyanate and a polyol is a diol. Waterproof material composition. The two-component room-temperature-curable hand-painted urethane waterproof material composition according to any one of claims 1 to 4 , wherein 70 equivalent % or more of the polyisocyanate is tolylene diisocyanate.