JP2018044068A - Quick-curable two-pack type urethane waterproof material composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a urethane waterproof material composition which is environmentally friendly, is excellent in quick curability and adhesiveness while securing sufficient workability throughout the year, and corresponds to an urethane rubber-based high elongation shape of JIS A 6021 (coating film waterproof material for building).SOLUTION: A urethane waterproof composition is composed of a main agent containing an isocyanate group terminal prepolymer formed of polyisocyanate and polyol and a curing agent containing aromatic polyamine and a plasticizer, where the main agent contains a tolylene diisocyanate skeleton and an isophorone diisocyanate skeleton in a molar ratio of 50/50 to 97/3, and the curing agent contains diethyl toluenediamine as aromatic polyamine and 4,4'-methylene bis(N-sec-butylaniline) in an equivalent ratio of 40/60 to 97/3.SELECTED DRAWING: None

Description

  The present invention relates to a fast-curing two-component urethane waterproof material composition and a method for producing the same.

Two-component urethane waterproof material is suitable for construction of irregular shapes and narrow parts, and is also economical, so it is widely used for roofing waterproofing of concrete buildings including verandas and fences. Has been developed.
Two-component urethane waterproofing material is applied on the construction site after mixing two liquids of the main agent and curing agent with a stirrer for several minutes, and then applied with a gold trowel, comb spatula, rubber spatula, roller, brush, etc. The curing reaction starts at the same time as mixing starts, and the viscosity gradually increases. After passing through a low-viscosity state (hereinafter referred to as pot life) that is easy to apply for a certain period of time, it becomes highly viscous and hard to be applied. To go. The pot life is preferably at least about 30 minutes or more at the actual construction temperature, and the time until the viscosity at 23 ° C. reaches 60,000 mPa · s is used as an index for convenience.

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 until the worker can get on the coating film to perform the next process (below) , Also called construction possible time). In normal work, it is desired that the urethane waterproofing material is applied in the evening, and the next day morning it is desired to be ready for construction, and the construction possible time is preferably adjusted within about 17 hours throughout the year. .
In the construction in summer, the temperature of the material rises to about 35 ° C. and the reactivity increases. Therefore, in order to ensure a 30 minutes pot life, the pot life at 23 ° C. is preferably about 50 minutes or more, For this purpose, appropriate blending techniques are required. On the other hand, in winter, since the material temperature is lowered to about 5 ° C. and the reactivity is lowered, it is relatively easy to secure the pot life, and there is no problem if the pot life at 23 ° C. is about 25 minutes or more. In order to make it curable by the next morning, it is necessary to have an appropriate blending technique. Therefore, it is general that the two-pack type urethane waterproof material is prepared in at least two kinds of blends for summer and winter, and ensures the pot life and workable time according to each season.

  The two-component urethane waterproofing material that is currently widely used is mainly composed of an isocyanate group-terminated prepolymer composed of tolylene diisocyanate (hereinafter referred to as TDI) and polyoxypropylene polyol, and in one curing agent, A low-reactivity secondary polyol using 3,3'-dichloro-4,4'-diaminodiphenylmethane (hereinafter referred to as MOCA), which is an aromatic polyamine having a relatively mild reaction as an active hydrogen component, as a main component. The polyoxypropylene polyol which is is used together. At that time, in the curing agent, as a promoter, it is common to use lead carboxylate, which is said to have an anti-foaming effect by selectively accelerating the reaction with polyol rather than moisture. Such a waterproof material is called a MOCA cross-linked waterproof material.

MOCA cross-linked waterproof material is mild in reactivity, so it has excellent workability especially in summer when pot life is required, and it has relatively good mechanical strength. It is used. On the other hand, MOCA crosslinkable waterproofing material has poor curability at low temperatures, so it is common to add lead carboxylate as an accelerator in winter, but there is a limit to improving low-temperature curability, Furthermore, the problem that heat resistance deterioration is accelerated | stimulated by mix | blending many lead compounds also expresses.
In addition, there is a method using a carboxylic acid such as 2-ethylhexanoic acid as an accelerator, but the reaction between MOCA and isocyanate is promoted, but the reaction with the polyol used in combination is not promoted. There are still limits to improvement.

The MOCA cross-linked waterproof material also has a serious 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 (showing 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 used as an accelerator is a material that is severely restricted worldwide, and is designated as a specified type 1 designated chemical substance in the Chemical Substance Emission Control Management Promotion Law (commonly known as the PRTR Law). It is a material that you want to avoid from an environmental point of view.

In a two-component urethane waterproof material, it is called a DETDA cross-linked waterproof material using diethyltoluenediamine (hereinafter referred to as DETDA), which is more reactive than MOCA and highly safe for the TDI prepolymer. Types are also commercialized. DETDA cross-linkable waterproofing material has a characteristic that it has good curability even at low temperatures, but it is necessary to add a large amount of plasticizer in order to ensure the pot life in summer. However, if too much plasticizer is used, problems such as poor adhesion to the top coat and increased plasticizer migration occur, so there is a limit to the amount used, and it is considered difficult to secure the pot life in summer. Yes.
As a method for securing the pot life of the DETDA cross-linked waterproof material, a method using a special TDI (Patent Document 1) and isophorone diisocyanate (hereinafter referred to as IPDI) which is a low-reactivity polyisocyanate. A method of using together with TDI (patent document 2), a method of using 4,4′-methylenebis (N-sec-butylaniline), which is a mild reactive secondary amine, and DETDA (patent document 3), etc. Although it has been proposed, problems still remain in each method, and it has not yet been generalized.

In addition, since DETDA is considerably more reactive than moisture, the coating film containing DETDA as a main reaction component has an advantage that the foaming phenomenon can be suppressed without lead carboxylate, which is further advantageous in terms of environment. .
In addition, unlike the MOCA cross-linkable waterproof material, DETDA cross-linkable water-proof material can be further improved in curability by using a curing accelerator in winter, but the work life is also reduced because the pot life is still shortened. End up. Therefore, although a curing accelerator is not usually used, curing can be accelerated by a carboxylic acid lead compound such as lead 2-ethylhexanoate or a low molecular carboxylic acid such as 2-ethylhexanoic acid.
The curing accelerator is generally blended on the curing agent side because no problem occurs in storage stability, but it is also added at the construction site as the third component. When added at the construction site, there is the convenience that the added amount can be adjusted according to the temperature at the time of construction, but there is a problem that mixing errors are likely to occur because the added amount is small, storage and management There is also the problem that it is difficult.

  The coating performance of the urethane waterproof material is specified not only in mechanical strength but also in weather resistance, heat resistance, acid resistance, alkali resistance, etc. in JIS A 6021 and satisfies this JIS standard. Otherwise, it will not be accepted by government offices, and of course it will not be accepted as a product.

  In addition, in a general urethane waterproofing method, a primer for ensuring adhesion is applied to an inorganic base such as concrete, and after the primer is cured, a urethane waterproofing layer is applied, and then weather resistance is ensured. It is common to apply a top coat to the top. In addition, with respect to a relatively large area inorganic base material, a ventilation cushioning method in which various ventilation cushioning sheets are applied, a urethane waterproof material is applied thereon, and then a topcoat is applied is widespread.

In any construction method, the urethane waterproof layer is generally applied in two times in order to compensate for defects in the coating film and ensure uniformity, and finally the film thickness is 2 mm to 3 mm. A simple construction method in which a urethane waterproof layer is applied 1-2 mm at a time and then a top coat is applied is also spread to some extent on construction sites such as verandas, scissors and skirting boards.
At present, if one layer of urethane waterproof material is applied, it will not harden on the day, so the next process such as applying the second layer of urethane waterproof material or top coat is usually performed the next day. It is regarded as a drawback of the urethane waterproof material that it becomes longer. Furthermore, in recent years, there has been a tendency for climate change to become severe, and there has also been a problem that the uncured urethane waterproof layer is damaged due to rain within a few hours after applying the urethane waterproof material.

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

Recently, the shortage of construction workers has become remarkable, and there is a demand for a waterproofing method and a waterproofing material that are more efficient and labor-saving in the waterproofing industry. In particular, the urethane waterproof material requires a work period of 3 to 5 days even for a small-area construction, and there remains a big problem that the work period is further extended if the weather is not good.
In addition, if rain is expected at night, urethane waterproofing material cannot be applied even if the weather is sunny, and the coating was damaged by rain because it was forcibly applied before raining, There is also a problem that a great deal of time and labor is spent on repairs.

DETDA cross-linkable waterproofing materials have been studied mainly for waterproofing materials that can be cured in about 5 hours after construction (can be constructed) and can move to the next process during the day, but can be used if the construction time is shortened. Since the time is shortened at the same time and the construction becomes difficult, it is limited to a special application such as a minimum area or for repairing, and has not been widely used.
In addition, the DETDA cross-linking waterproof material still has a problem that the adhesion to the primer and the adhesion between the waterproof materials are not sufficient.
General-purpose MOCA cross-linked waterproof materials have problems of poor curability at low temperatures and insufficient environmental response, and can be cured during the day throughout the year. A fast-curing urethane waterproof material having the same pot life, good adhesion and workability, and environmentally friendly is desired.

In DETDA cross-linked waterproof material, when used together with 4,4'-methylenebis (N-sec-butylaniline), which is an aromatic secondary amine that is milder than DETDA, it can be used for a long time without degrading the curability. Can be extended to a relatively fast-curing waterproof material, but by using 4,4'-methylenebis (N-sec-butylaniline), heat resistance and alkali resistance are drastically reduced. Therefore, the problem of lack of practicality occurs.
On the other hand, it has been pointed out that the use time can be extended to some extent by using TDI and IPDI together in the main agent, but the physical properties and curability are lowered.

  As a result of further detailed examination of the above points, the present application uses TDI and IPDI in a specific range as main agents, and DETDA and 4,4'-methylenebis (in a specific range in the presence of a plasticizer as a curing agent. N-sec-Butylaniline) makes it fast-curing while maintaining the pot life, is excellent in heat resistance and alkali resistance, and has good adhesion with the primer and adhesion between waterproof materials. And found that it becomes an environment-friendly fast-curing waterproofing material. Furthermore, the above composition is suitable for a fast-curing waterproofing material formulated for summer that requires a pot life, but by using an acid anhydride as a curing accelerator in this composition, the pot life can be reduced even at low temperatures. It turned out that it becomes the quick-cure waterproofing material which hold | maintained.

  In addition, since the reaction rates of TDI and IPDI are greatly different in the production method of the main agent, a method of separately producing TDI prepolymer and IPDI prepolymer and blending both is known (Patent Document 2). However, in the present invention, TDI and IPDI can be charged at the same time or IPDI and polyol can be charged first and then the reaction can be carried out to some extent before TDI is charged, which can greatly improve productivity. I understood.

The present invention includes the following aspects.
[1] A two-component urethane waterproofing composition comprising a main agent containing an isocyanate group-terminated prepolymer composed of a polyisocyanate and a polyol, and a curing agent containing an aromatic polyamine and a plasticizer, the main agent being tolylene diisocyanate It contains a skeleton of narate and isophorone diisocyanate in a molar ratio of 50/50 to 97/3, and the curing agent is 40/50 of diethyltoluenediamine and 4,4'-methylenebis (N-sec-butylaniline) as an aromatic polyamine. A two-component urethane waterproofing composition comprising an equivalent ratio of 60 to 97/3.
[2] The two-component urethane waterproofing composition according to [1], wherein 80 equivalent% or more of the active hydrogen component in the curing agent is an aromatic polyamine.
[3] The two-component urethane waterproofing composition according to [1] or [2], which contains an acid anhydride as a curing accelerator.
[4] A method for producing a two-pack type urethane waterproofing composition comprising a main agent containing an isocyanate group-terminated prepolymer comprising a polyisocyanate and a polyol, and a curing agent containing an aromatic polyamine and a plasticizer, Is
Tolylene diisocyanate, isophorone diisocyanate and polyol are reacted in the same vessel in a molar ratio of tolylene diisocyanate and isophorone diisocyanate in the range of 50/50 to 97/3 to give an isocyanate group-terminated prepolymer. Preparing a base comprising: and
Diethyltoluenediamine, 4,4′-methylenebis (N-sec-butylaniline) and a plasticizer are used, and the equivalent ratio of diethyltoluenediamine and 4,4′-methylenebis (N-sec-butylaniline) is 40/60 to 97. In the range of / 3, the method of mixing and preparing a hardening | curing agent is included.
[5] The process according to [4], wherein the step of preparing the main agent includes a step of reacting isophorone diisocyanate and polyol in a container, and then a step of adding tolylene diisocyanate to the container and further reacting. the method of.

The two-pack type urethane waterproofing material composition of the present invention is a fast-curing waterproofing material that has a sufficient pot life in the summer, and has a low-temperature curability that has a pot life in the winter. It becomes a curable waterproof material, which enables shortening the construction period and improving the efficiency of construction throughout the year.
Further, it is an environment-friendly fast-curing urethane waterproof material with good productivity, which has good heat resistance and alkali resistance, and excellent adhesion to a primer and adhesion between waterproof materials.

In general, the pot life of the summer waterproofing material is preferably 50 minutes or more in the measurement at 23 ° C, and the workable time is preferably about 20 hours at 23 ° C. Cross-linked waterproofing is relatively easy to clear this goal.
On the other hand, the DETDA cross-linkable waterproofing material exhibits fast curability of about 5 to 7 hours, but it is difficult to make the pot life 50 minutes or more. In particular, when a general-purpose product called T-80 containing 2,4-TDI and 2,6-TDI at 80/20 (equivalent ratio) is used as the main polyisocyanate, the pot life is reduced. It becomes difficult to secure. A special product called T-100 containing 100% 2,4-TDI is advantageous for securing the pot life, but the supply amount is limited. Is not suitable.

  As the isocyanate group-terminated prepolymer of the main agent, the combined use time can be extended to some extent by using a TDI prepolymer and an IPDI prepolymer together (Patent Document 2). A decrease is pointed out, and there is also a problem that the productivity is lowered because it is necessary to blend and produce two kinds of prepolymers.

  In one curing agent, the use of 4,4'-methylenebis (N-sec-butylaniline), a low-reactivity aromatic secondary amine, together with DETDA is an effective method for extending the pot life ( Patent Document 3), and the combined use of 4,4'-methylenebis (N-sec-butylaniline) within a certain range shows the property that the curability is not impaired so much, so that the usable time can be extended without significantly impairing the rapid curing property. Can be made possible. However, the use of 4,4'-methylenebis (N-sec-butylaniline) causes a large practical problem that the heat resistance and alkali resistance are extremely lowered simultaneously with the deterioration of physical properties.

  As a result of the detailed examination of the DETDA cross-linked waterproof material again, the present invention has a tolylene diisocyanate skeleton (hereinafter also referred to as “TDI skeleton”) and an isophorone diisocyanate skeleton (hereinafter also referred to as “IPDI skeleton”). )) In a specific range, and DETDA and 4,4'-methylenebis (N-sec-butylaniline) as the aromatic polyamine component of the curing agent in a specific range. The present inventors have found that it becomes a fast-curing waterproofing material that can ensure a longer pot life than conventional ones.

ＩＰＤＩ骨格とは式（２）に示す分子構造を言う。

The TDI skeleton refers to the molecular structure shown in Formula (1),

The IPDI skeleton refers to the molecular structure shown in Formula (2).

It is expected that the pot life will be extended by using IPDI as the main agent and 4,4'-methylenebis (N-sec-butylaniline) at the same time as the curing agent. It has been found that heat resistance and alkali resistance, which are the biggest problems with using -methylenebis (N-sec-butylaniline), tend to be improved.
In addition, the curability tends to be delayed by the combined use of IPDI, but the fast curability that is a feature of the DETDA cross-linking type is maintained, so that it becomes a quick-curing waterproof material that maintains the pot life in the summer. If the temperature is around 30 ° C., it can be constructed in about 5 hours, and two processes per day are possible.
Further, by using IPDI in combination with the main agent, it is possible to improve the adhesion with the primer and the adhesion between the waterproofing materials, and in this respect as well, the weaknesses of the DETDA crosslinked waterproofing material can be improved.

(Main agent)
In the present invention, the main agent needs to contain a TDI skeleton and an IPDI skeleton in a molar ratio of 50/50 to 97/3, preferably a molar ratio of 60/40 to 95/5, and a molar ratio of 70/30 to 90/10. The ratio is more preferable. If the molar ratio of the IPDI skeleton exceeds 50, it will be difficult to be a fast-curing waterproof material, and if it is less than 3, it will be a fast-curing waterproof material with good heat resistance and alkali resistance with good working life. hard.

(Polyisocyanate)
Polyisocyanates for introducing a TDI skeleton into the main agent include T-65 having an equivalent ratio of 2,4-TDI to 2,6-TDI of 65/35 and 80/20, which are industrially available. T-100 which is -80, 100/0 can be used, and each blended product can also be used. However, since T-100 and T-65 are manufactured by separation and purification from T-80, which is an industrially general-purpose product, the production amount is limited. Although T-100 is advantageous from the viewpoint of securing the pot life, it is preferable to use T-80 as a main component for use in a versatile urethane waterproof material. Moreover, if it is a part, derivatives, such as a dimer body of TDI, a nurate body, an allophanate body, can be used. Preferably, all of the TDI skeleton is derived from TDI monomers.

  As the polyisocyanate for introducing the IPDI skeleton into the main agent, IPDI monomers, nurate bodies, adduct bodies, allophanate bodies and other IPDI derivatives can be used. Preferably, the IPDI skeleton is derived from IPDI monomers.

  In the present invention, an IPDI monomer or an IPDI derivative can be added to the TDI prepolymer. However, for the effect of improving the adhesion with the primer and the adhesion between waterproofing materials and the effect of extending the pot life, It is effective to use IPDI as a prepolymer. Therefore, it is preferable to use TDI and IPDI as prepolymers for the main agent of the present invention.

  Other polyisocyanates can also be used in combination, but the isocyanate group is preferably less than 30 equivalent%, more preferably less than 20 equivalent%, and less than 10 equivalent%. Is more preferable. When other polyisocyanates are 30 equivalent% or more, it is difficult to become a fast-curing waterproofing material having a working life. Other polyisocyanates include hexamethylene diisocyanate, norbornene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated tetramethylxylylene diisocyanate. And polyisocyanates having low reactivity such as xylylene diisocyanate, tetramethylxylylene diisocyanate, and diphenylmethane diisocyanate.

(Isocyanate content)
The isocyanate content of the main agent is preferably 1.5% by mass to 4.5% by mass, and more preferably 1.7% by mass to 4.0% by mass. If the isocyanate content is less than 1.5% by mass, the curability is lowered and it becomes difficult to obtain the physical properties required for the waterproof material, and if it exceeds 4.5% by mass, it is difficult to ensure the pot life.

(Polyol used for the main agent)
As the polyol used as the main agent, the polyols usually used as the main agent of urethane waterproofing materials can be used, but in order to make the main agent having a low viscosity and good workability, a polyoxypropylene polyol having a molecular weight of 300 to 8000 or It is preferable to use a polyether-based polyol such as oxyethylene polyoxypropylene polyol. Also, 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 also be used.

  Also, as a polyol, heat resistance and alkali resistance tend to be insufficient only with a diol, and when the polyol having a functional group number equal to or greater than triol is 80 equivalent% or more, it becomes difficult to ensure the pot life and elongation. Therefore, it is preferable to use a polyol having a functional group number equal to or greater than triol in the range of 3 to 80 equivalent%.

(Main agent NCO group / OH group equivalent ratio)
It is preferable to blend the polyisocyanate and the polyol so that the equivalent ratio of NCO group to OH group of the main agent and NCO group / OH group is in the range of 1.5 to 2.3. If the NCO group / OH group is less than 1.5, the viscosity of the main agent increases, and it becomes difficult to form a waterproof material with good physical properties. If it exceeds 2.3, free TDI or IPDI increases, and it becomes difficult to ensure the pot life.
Further, the NCO group / OH group is more preferably 1.5 to 2.1, the content of free TDI in the main agent can be 1% or less, and the total amount of free TDI and free IPDI is also 1%. Since it can be as follows, it can be an environmentally friendly waterproof material.

(Manufacturing method of main agent)
Since there is a big difference in reactivity between TDI and IPDI, the “mixing” method in which TDI prepolymer and IPDI prepolymer are produced separately and blended together is generally used. The effect of improving the adhesiveness is high, there is an effect of extending the pot life, and the effect of improving the heat resistance and alkali resistance can also be confirmed. However, since this method requires two separate synthesis steps and a blending step, it requires a lot of production equipment and time, which impairs economy.

  As a result of further investigation, it was found that batch production using the same reaction vessel was possible. First, in the “batch charging” method in which TDI and IPDI are charged almost simultaneously, for example, when a reaction is carried out at around 100 ° C., IPDI monomer that is low in reactivity reacts partially after the TDI prepolymer is produced. The effect of extending the pot life and the effect of improving the adhesion between the primer and the waterproof material were clarified, and the heat resistance and alkali resistance were also improved. However, when the amount of the remaining monomer of IPDI increases, it becomes difficult to ensure the pot life and the physical properties.

  Next, the “two-stage charging” method in which IPDI was charged first and the reaction with polyol was advanced to some extent before TDI was charged was examined. Since the reaction of IPDI and polyol in the first stage has a large excess of hydroxyl groups, for example, at a reaction temperature of 100 ° C., about 50% of all isocyanate groups of IPDI reacted in about 8 to 10 hours. By this method, the IPDI monomer can be reduced. In addition, polyols can be blended separately. After that, when TDI is charged as the second stage and the reaction is started at 100 ° C., for example, the isocyanate group of TDI, which is more reactive than IPDI, seems to preferentially react with the polyol. Can be reacted. In this method, the secondary isocyanate group of IPDI, which is ultimately low in reactivity, seems to remain in a considerable amount, and the working life extension effect, primer, or waterproofing material is almost the same as the conventional “mixing” method. It was found that the effect of improving the adhesion between each other was obtained, and the heat resistance and alkali resistance were also good.

Furthermore, as a result of examining the above-mentioned “two-stage charging” method, it is possible to shorten the reaction time or lower the reaction temperature by using a urethanization catalyst in the reaction between the first stage IPDI and the polyol. Moreover, it was found that the reaction rate in the first stage can be sufficiently controlled.
As the urethanization catalyst, general urethanization catalysts such as tertiary amines, acids, carboxylic acid metal salts, and tin compounds can be used. In particular, dioctyltin dilaurate and dibutyltin dilaurate which are organic stannic compounds. It is preferable that the reaction time of the first stage can be shortened, and further, the reaction can be rapidly advanced even at a low temperature around 60 ° C. The amount of organic stannic used is preferably 0.0001 to 0.1% by mass with respect to the total amount of IPDI and polyol, and the reaction temperature is preferably 40 to 110 ° C.

Further, when the reaction in the first stage reaches an arbitrary reaction rate, the reaction can be almost stopped by adding a material that deactivates the urethanization catalyst such as phosphoric acid. Addition has the effect of preventing runaway reaction due to side reactions such as allophanatization during the reaction with the second stage TDI, and the reaction can proceed safely and smoothly.
Examples of the deactivator for the urethanization catalyst include inorganic acids, chlorinated acidic substances such as benzoyl chloride and phthalic acid chloride, among which phosphoric acid is effective and preferable. The amount of phosphoric acid used depends on the amount of urethanization catalyst used, and is preferably 50 to 200 equivalent% with respect to the urethanization catalyst.

The first stage reaction is preferably carried out in the range of 10 to 75% of the total isocyanate groups of IPDI, and more preferably in the range of 20 to 60%. If the reaction rate is less than 10%, a large amount of IPDI monomer remains in the end, so that the effect of extending the pot life and the effect of improving the adhesiveness are insufficient. Since the number of nate groups decreases, the effect of extending the pot life, the effect of improving the adhesiveness, and the effect of improving the heat resistance and alkali resistance become insufficient.
The above-mentioned “two-stage charging” method is more effective than the “collective charging” method in which TDI and IPDI are simultaneously charged in securing the working life, improving adhesion with the primer, and adhesion between waterproofing materials. Since alkalinity is also favorable, it becomes a more preferable production method in the present invention.

(Main agent NCO / Hardening agent NH ₂ equivalent ratio)
The main agent NCO / curing agent NH ₂ , which is the equivalent ratio of the isocyanate group of the main agent to the amino group of the aromatic polyamine of the curing agent, is preferably 0.9 to 1.8. If the main agent NCO / curing agent NH _{2 in the} two-liquid mixing is less than 0.9, the high molecular weight is insufficient and the physical properties are lowered, and if it exceeds 1.8, the curability is lowered and the physical properties are also insufficient.

(Hardener active hydrogen compound)
This application needs to contain DETDA and 4,4'-methylenebis (N-sec-butylaniline) as an aromatic polyamine in an equivalent ratio in the range of 40/60 to 97/3, and 50/50 to 95/5. The range is preferable, and the range of 60/40 to 90/10 is more preferable. When the equivalent ratio of 4,4′-methylenebis (N-sec-butylaniline) to DETDA exceeds 60, it becomes difficult to maintain physical properties, heat resistance and alkali resistance at the same time as it is not fast-curing. The effect of extending the pot life is insufficient.
In DETDA, there are isomers such as 3,5-diethyl-2,4-toluenediamine and 3,5-diethyl-2,6-toluenediamine. In the present application, any isomer may be used. Or mixtures thereof may be used. For industrial use, for example, Etacure 100 (mass ratio of 2,4-isomer / 2,6-isomer 80/20) manufactured by Albemarle is available. As 4,4′-methylenebis (N-sec-butylaniline), Etacure 420 manufactured by Albemarle Co., Ltd. is available.

  Other aromatic amines can be used as long as they are a part, but it is preferably 30 equivalent% or less with respect to the total amount of DETDA and 4,4′-methylenebis (N-sec-butylaniline). More preferably, it is 20 equivalent% or less. When the amount of other aromatic polyamines exceeds 30 equivalent%, it is difficult to become a fast-curing waterproofing material that maintains the pot life.

  Other aromatic polyamines that can be used include Cure Hard MED (4,4'-methylenebis (2-ethyl-6-methylaniline)) manufactured by Ihara Chemical Industry Co., Ltd., which is highly reactive in the same manner as DETDA. Kayahard AA (4,4'-methylenebis (2-ethylaniline)) manufactured by Yakuhin 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. can be mentioned, but since the crystallinity is often high or the solubility is poor, It is preferable to make it less than 30 equivalent% in aromatic polyamine.

  Further, as low-reactivity aromatic polyamines, ethacur 300 (dimethylthiotoluenediamine) manufactured by Albemarle, Elastomer 650P (polytetramethylene glycol bis (p-aminobenzoate)) manufactured by Ihara Chemical Co., Ltd., Ihara Chemical Co., Ltd. Polea SL-100A (poly (tetramethylene / 3-methyltetramethylene ether) glycol bis (4-aminobenzoate)) and the like manufactured by the manufacturer can be mentioned, but since the rapid curing tends to be impaired when the amount used is increased, Again, it is preferable to make it less than 30 equivalent% in the aromatic polyamine.

  In this application, it is preferable that 80 equivalent% or more of the active hydrogen component in a hardening | curing agent is an aromatic polyamine, and it is more preferable that it is 90 equivalent% or more. If the other active hydrogen component exceeds 20 equivalent%, sufficient pot life and fast curability cannot be obtained.

If the polyol is also 20 equivalent% or less as an active hydrogen component in the curing agent, it can be used for adjustment of pot life, viscosity adjustment, wetness adjustment, physical property adjustment, adhesion improvement and the like.
Examples of the polyol that can be used include relatively high molecular weight polyols such as polyoxypropylene polyol, polyoxyethylene polyoxypropylene polyol, and polyester polyol, 1,4-butanediol, 1,6-hexanediol, and 3-methyl-1,5. Short chain polyols such as pentanediol, trimethylolpropane and glycerin can also be used.

(Plasticizer)
In order to ensure the pot life, it is necessary to use a plasticizer. It is preferable to use 20 to 90 parts by mass of a plasticizer with respect to 100 parts by mass of the prepolymer in the main agent. It is more preferable to use a part. If the plasticizer is not used, the pot life cannot be secured. The plasticizer is preferably blended in the curing agent, but may be partially blended on the main agent side.

  As the plasticizer, a plasticizer that can be generally blended in a urethane resin can be used. Examples include phthalate esters such as diisononyl phthalate (DINP), dioctyl phthalate (DOP), butyl benzyl phthalate (BBP), aliphatic dibasic acid esters, phosphate esters, trimellitic acid esters, Examples include sebacic acid esters, epoxy fatty acid esters, glycol esters, animal and vegetable oil fatty acid esters, petroleum / mineral oil plasticizers, and alkylene oxide polymerization plasticizers. Among them, diisononyl phthalate (DINP) and dioctyl phthalate (DOP) having a flash point of 200 ° C. or higher are preferably used because they are less likely to cause weight loss over the long term, and are aromatic polyesters and hardly hydrolyze. be able to.

(Inorganic filler)
In the present application, it is preferable to use an inorganic filler. By blending an inorganic filler, a fast-curing waterproof material having a sufficient pot life can be made into physical properties conforming to JIS standards, and an economical waterproof material can be obtained. The filler is preferably blended in the curing agent, but may be partially blended on the main agent side. It is preferable that the compounding quantity of an inorganic filler is 20 mass parts-80 mass parts in a hardening | curing agent. If the filler is less than 20 parts by mass, the reinforcing effect tends to be insufficient, and if it exceeds 80 parts by mass, the physical properties are lowered and the viscosity is likely to increase due to a decrease in the resin content.

  Examples of the filler include calcium carbonate, which has good dispersibility during production, can easily maintain a relatively low viscosity state even when the amount is increased, and has a high cost reduction effect. Calcium carbonate includes heavy calcium carbonate, light calcium carbonate, colloidal calcium carbonate, various surface-treated calcium carbonates, and any calcium carbonate can be used. Moreover, since moderate thixotropy is obtained by mix | blending surface treatment colloidal calcium carbonate, the waterproofing material for elevations can also be manufactured. As other inorganic fillers, silica-based, kaolin clay-based, talc-based, bentonite-based, etc. can be used, but as the amount used increases, there is a problem that the thickening becomes violent and the water content is difficult to manage, It is preferable that calcium carbonate is the main component. Moreover, if an organic type filler is also part, it can be used.

  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. Further, by blending a plasticizer on the curing agent side, a large amount of inorganic filler can be blended, and an economical waterproof material can be obtained.

  The urethane waterproof material of the present application is suitable not only for a flat field waterproofing material having leveling properties, but also for a vertical waterproofing material that has non-sag properties and can be applied to an upright portion or an inclined portion. The waterproofing material for elevations is a combination of many non-sag imparting agents such as surface-treated colloidal calcium carbonate, and it requires a longer pot life than the waterproofing material for flat fields in order to construct complex parts. It is possible to sufficiently cope with the above, and it is possible to exhibit fast curability.

  As described above, even in the summertime when the temperature is around 30 ° C., it is possible to provide a quick-curing waterproof material that has a pot life of 30 minutes or more and can be processed in the next 5 hours. The alkalinity is good, and at the same time, the adhesion with the primer and the adhesion between waterproofing materials can be improved. For summer use of general-purpose MOCA cross-linked waterproof material, the pot life at 30 ° C can be 30 minutes or more, and the part exposed to direct sunlight can be constructed in about 5 hours. In many cases, the construction time is about 7 to 10 hours, and it is difficult to perform the two steps a day because it is difficult to be as fast as the present application.

(Curing accelerator)
Next, a detailed study was conducted on the use of the fast-curing waterproofing material that has secured the pot life as described above throughout the year. The conventional DETDA cross-linkable waterproofing material has relatively good low-temperature curability, but if it is allowed to be constructed in about 5 hours at a low temperature of about 10 ° C., the pot life is 30 minutes or less. Sexuality will deteriorate. In order to improve the curability of the conventional DETDA crosslinked waterproofing material, a method of increasing the amount of DETDA used, a method of reducing the plasticizer, a metal carboxylate such as lead 2-ethylhexanoate as an accelerator, Although the method etc. which use carboxylic acids, such as 2-ethylhexanoic acid, are mentioned, any method will shorten a pot life significantly.

However, as a result of examining various possibilities, when an acid anhydride is used as a curing accelerator in the composition of the present invention, it plays a role in promoting curability without reducing the pot life so much, even at low temperatures. It has been found that it exhibits fast curability.
An acid anhydride is considered to generate a carboxylic acid group by an addition reaction with an active hydrogen group such as an amino group such as DETDA in a curing agent, a hydroxyl group of a polyol, or moisture in a curing agent, and expresses a curing accelerating action. At that time, the addition reaction between the acid anhydride and the active hydrogen group is not instantaneous, but seems to have a moderate reaction rate, and as a result, the carboxylic acid group gradually increases, so that it can be used for several tens of minutes. Although it has little influence on time, it is presumed that it effectively acts on the curability after several hours and exhibits the effect of a latent accelerator.

  The present invention relates to a conventional curing accelerator such as a low molecular carboxylic acid such as 2-ethylhexanoic acid or a carboxylic acid metal salt such as zinc 2-ethylhexanoate or lead 2-ethylhexanoate. However, it is preferable to use an acid anhydride that can exhibit fast curing properties as compared with a conventional accelerator and can exhibit rapid curability as a curing accelerator. The acid anhydride can also be used as a summer waterproof material, and although the pot life is slightly shortened, it can be used as a fast-curing waterproof material with good workability in spring and autumn.

The acid anhydride can be blended in advance on the curing agent side, but in that case, it reacts with the active hydrogen group in the curing agent over time, resulting in a state where a carboxylic acid group is generated. It has the same effect as acid and shortens the pot life. Therefore, in this application, the method of adding an acid anhydride to a main ingredient or when mixing a main ingredient and a hardening | curing agent is preferable. As a method of adding an acid anhydride when mixing a main agent and a curing agent, a main agent part including an isocyanate group-terminated prepolymer, a curing agent part including an aromatic polyamine and a plasticizer, and a curing including an acid anhydride are included. A method of preparing a kit of accelerator parts and mixing those parts at the 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.

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 anhydride, 3-methylhexa Hydrophthalic 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 anhydride, ethylene glycol bisanhydro trimellitate, glycerin bis Hydrotrimellitate 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 and the like. .
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.) 4-methyl-1,2,3,6-tetrahydrophthalic anhydride mixture), Rikacid HH (hexahydrophthalic anhydride) manufactured by Shin Nippon Rika Co., Ltd., Rikacid MH-700 (3- Methylhexahydrophthalic anhydride / 4-methylhexahydrophthalic anhydride = 70/30 mixture), Rikacid MH (4-methylhexahydrophthalic anhydride) manufactured by Shin Nippon Rika Co., Ltd. Ricacid HNA-100 (methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride and bicyclo [2.2.1] heptane-2, -A mixture of dicarboxylic anhydrides), MHAC-P (methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride) manufactured by Hitachi Chemical Co., Ltd., DSA manufactured by Sanyo Chemical Industries, Ltd. (Tetrapropenyl succinic anhydride), Rikacido OSA (octenyl succinic anhydride) manufactured by Shin Nippon Rika Co., Ltd., and the like. Among them, HN-2200 (3-methyl-1,2,3 manufactured by Hitachi Chemical Co., Ltd.) is particularly mentioned. , 6-Tetrahydrophthalic anhydride and 4-methyl-1,2,3,6-tetrahydrophthalic anhydride), MHAC-P (Methyl-3,6-endomethylene-1,2, manufactured by Hitachi Chemical Co., Ltd.) , 3,6-tetrahydrophthalic anhydride), Rikacid MH-700 (3-methylhexahydrophthalic anhydride / 4-methylhexa) manufactured by Shin Nippon Chemical Co., Ltd. Mud mixture phthalic 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. 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 can be used. An imidazole compound which is a special tertiary amine is preferable. Examples of the imidazole compound include 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2- A compound having a substituent at the 1-position and the 2-position, such as phenylimidazole, and a compound having a substituent at the 1-position, such as 1-methylimidazole and 1-allylimidazole, can be used. Of these, imidazole compounds having substituents at the 1-position and 2-position are preferred. The tertiary amine is preferably used in an amount of 0.01 to 2.0% by mass in the curing agent.

  In addition, carboxylic acid metal salts that are generally urethane curing accelerators can also be 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 zirconium salts, tin salts, copper salts , Magnesium salt, calcium salt, strontium salt, barium salt and the like, and 0.1 to 4.0% by mass of the carboxylic acid metal salt is preferably used in the curing agent.

  Examples of the carboxylic acid include propionic acid, 2-methylpentanoic acid, 2-ethylhexanoic acid, isononanoic acid, naphthenic acid, and the like, among which 2-ethylhexanoic acid is preferable. It is desirable to use 0.05 to 2.0% by mass of the carboxylic acid in the curing agent, and a part or all of the carboxylic acid may be added to the main agent side.

(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.

Raw materials The raw materials used in the following examples and comparative examples are as follows.
[Isocyanate]
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 Nippon Polyurethane Industry Co., Ltd. [Polyol]
Sanniks PP-2000: Polyoxypropylene diol, average molecular weight 2000, OH value 56.1 mgKOH / g, Sanyo Chemical Industries, Ltd. Sanniks GH-3000: Polyoxypropylene triol, average molecular weight 3000, OH value: 56.1 mgKOH / G, Sanyo Chemical Industries, Ltd. [solvent]
MC-2000 solvent: normal paraffin, isoparaffin mixture, manufactured by Sankyo Chemical Co., Ltd. [polyamine]
DETDA: Etacure 100, diethyltoluenediamine, manufactured by Albemarle Japan Co., Ltd. Etacure 420: 4,4′-methylenebis (N-sec-butylaniline), aromatic secondary diamine, manufactured by Albemarle [catalyst]
Dioctyltin dilaurate: KS-1200A-1, manufactured by Kyodo Yakuhin Co., Ltd. 1-isobutyl-2-methylimidazole: DABCO NC-IM, manufactured by Air Products Japan Co., Ltd. Phosphoric acid: 85% phosphoric acid, manufactured by Nacalai Tesque, Inc. HN- 2200: 3- or 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, manufactured by Hitachi Chemical Co., Ltd. [plasticizer]
DINP: Sansosizer DINP, diisononyl phthalate, manufactured by Shin Nippon Rika Co., Ltd. [inorganic filler]
Calcium carbonate NS # 100: NS # 100, calcium carbonate, manufactured by Nitto Flour Industry Co., Ltd. [Additives]
Additives: Enomoto Kasei Co., Ltd. [Primer]
OT Primer M: One-component moisture-curing mediator primer, Tajima Roofing Co., Ltd. OT Primer A: One-component moisture-curing primer, Tajima Roofing Co., Ltd.

Preparation of Main Agent [Two-Stage Charge] Method According to the formulations shown in Tables 1 to 3 and 5, a four-necked flask was charged with a polyol, a solvent, IPDI and, if necessary, a catalyst. Thereafter, the mixture was reacted at a predetermined temperature for a predetermined time with stirring, and phosphoric acid was added as necessary after the reaction was completed. Further, T-80 was charged and reacted again at a predetermined temperature for a predetermined time to obtain a prepolymer.
[Batch Charge] Method According to the formulation shown in Table 4, a four-necked flask was charged with a polyol, a solvent, and polyisocyanates. Thereafter, the mixture was reacted at a predetermined temperature for a predetermined time with stirring to obtain a prepolymer.
[Mixing] Method According to the formulation shown in Table 4, a four-necked flask was charged with a polyol, a solvent, IPDI, and if necessary, a catalyst. Thereafter, the mixture was reacted at a predetermined temperature for a predetermined time with stirring to obtain an IPDI prepolymer. A T-80 prepolymer was similarly obtained using T-80 instead of IPDI. An IPDI prepolymer and a T-80 prepolymer were mixed at a predetermined ratio and used as a main agent.
Each prepolymer was used as a main agent by adding a plasticizer, a catalyst and the like as required.

Preparation of curing agent In accordance with the formulation of Tables 1 to 5, after the liquid material was charged into a metal container and mixed at low speed with a stirrer (dissolver blade) and uniformed, calcium carbonate was blended and mixed at 1500 rpm for 15 minutes to add each curing agent. Obtained.

Examples 1 and 2 (Table 1)
This is an example of summer blending using IPDI and T-80 as polyisocyanate and using a curing agent with 70/30 equivalent ratio of DETDA and Etacure 420 as synthesized by the “two-stage charging” method. . Example 1 in which the equivalent ratio of IPDI and T-80 is 20/80 shows good coating film properties as a waterproofing material and ensures sufficient pot life as a summer formulation, while the next process can be performed during the day. It was possible. In the interlayer adhesion test, the interlayer adhesion strength was strong enough to cause destruction of the urethane material without delamination. In addition, the adhesion test with the primer showed sufficient adhesive strength for practical use. Example 2 in which the equivalent ratio of IPDI and T-80 was 10/90 showed good coating film properties as a waterproof material and was able to be applied to the next process during the day while securing sufficient pot life. . Moreover, the interlayer adhesion test and the primer adhesion test showed a sufficient adhesive strength for practical use.

Comparative Example 1 (Table 1)
It is an example of the summer compounding which uses only T-80 as a polyisocyanate of the main ingredient to the hardening agent of the same composition as Examples 1 and 2. The pot life was 45 minutes, which was insufficient for summer use. Interlayer adhesion strength and primer adhesion strength were lower than those of Examples 1 and 2, and it seemed that there was a problem in practical use. Further, the tensile strength ratio after heat treatment or alkali treatment tended to be lower than in Examples 1 and 2. In particular, the tensile strength ratio after alkali treatment was as low as 71%, which seemed to be problematic in practical use.

Examples 3 and 4 (Table 2)
This is an example of summer blending using IPDI and T-80 as polyisocyanate, and a main agent synthesized by the “two-stage charging” method and a curing agent with an equivalent ratio of DETDA and Etacure 420 of 60/40. . Examples 3 and 4 having an equivalent ratio of IPDI and T-80 of 20/80 and 10/90, respectively, showed good film properties as a waterproofing material, and secured sufficient pot life as a summer formulation. The next process could be built inside. In the interlayer adhesion test, the adhesive strength was sufficient for practical use.

Comparative Example 2 (Table 2)
This is an example of summer blending using only T-80 as the main polyisocyanate for the curing agent blended in the same manner as in Examples 3 and 4. The pot life was 64 minutes, which was sufficient for summer use, but the interlayer adhesion strength was lower than in Examples 3 and 4, and it seemed that there was a problem in practical use. In addition, the tensile strength ratio after heat treatment or alkali treatment tended to be lower than in Examples 3 and 4. In particular, the tensile strength ratio after alkali treatment was as low as 65%, which seemed to be problematic in practical use.

Examples 5, 6, and 7 (Table 3)
Equivalent ratio of DETDA and Etacure 420, based on a main polymer obtained by adding 1.00 mass% of acid anhydride catalyst HN-2200 to a prepolymer synthesized by the “two-stage charging” method using IPDI and T-80 as polyisocyanate It is an example of the formula for winter using the hardening | curing agent which made 80/20. Examples 5, 6 and 7 having equivalent ratios of IPDI and T-80 of 30/70, 20/80 and 10/90, respectively, showed good coating properties as waterproofing materials and sufficient pot life for winter use During the day, the next process could be constructed while ensuring In the interlayer adhesion test, the adhesive strength was sufficient for practical use.

Comparative Example 3 (Table 3)
It is an example of the formula for winter which uses only T-80 as a polyisocyanate of a main ingredient with respect to the hardening | curing agent of the same mixing | blending as Example 5, 6, 7. FIG. The pot life was 24 minutes, which was insufficient for winter use. Interlayer adhesion strength was lower than in Examples 5, 6, and 7, and it seemed that there was a problem in practical use. In addition, the tensile strength ratio after the heat treatment or after the alkali treatment tended to be lower than those in Examples 5, 6, and 7.

Example 8 (Table 4)
It is an example of the formula for winter which synthesize | combined the main ingredient of the same composition as Example 7 by the "batch preparation" method. Example 8 showed good coating film properties as a waterproofing material, and was able to perform the next process during the day while securing sufficient pot life as a winter formulation. In the interlayer adhesion test, the adhesive strength was sufficient for practical use.

Example 9 (Table 4)
Example of winter blending using IPDI prepolymer and T-80 prepolymer separately and “mixed” main component so that the equivalent ratio of IPDI and T-80 is 10/90 as in Example 7 is there. Example 9 showed good film properties as a waterproofing material, and the next process could be performed during the day while securing sufficient pot life as a winter formulation. In the interlayer adhesion test, the adhesive strength was sufficient for practical use.

Examples 10, 11, 12 (Table 5)
This is an example of winter blending using a catalyst when synthesizing a prepolymer with the same blending as in Example 6 by the “two-stage charging” method. In Example 10 in which 0.0015% by mass of dioctyltin dilaurate was used as a catalyst in the reaction with the first stage IPDI, the first stage reaction proceeded rapidly at 60 ° C., which was lower than in Example 6. Thereafter, 0.0015% by mass of phosphoric acid was added to deactivate the catalyst, and the reaction with the second stage T-80 was carried out. Using the resulting prepolymer, a waterproofing composition was prepared in the same manner as in Example 6. As a result, while exhibiting good coating film properties and ensuring sufficient pot life as a winter formulation, Construction of the process was possible. In the interlayer adhesion test, the adhesive strength was sufficient for practical use.
In Example 11 in which 0.04% by mass of phosphoric acid was used as a catalyst in the reaction with the first stage IPDI, the first stage reaction proceeded rapidly at 100 ° C. and reached the desired conversion rate in a shorter reaction time than in Example 6. Reached. Furthermore, the reaction with the second stage T-80 also proceeded rapidly at 100 ° C. Using the resulting prepolymer, a waterproofing composition was prepared in the same manner as in Example 6. As a result, while exhibiting good coating film properties and ensuring sufficient pot life as a winter formulation, Construction of the process was possible. In the interlayer adhesion test, the adhesive strength was sufficient for practical use.
In Example 12, in which 0.10% by mass of 1-isobutyl-2-methylimidazole was used as a catalyst in the reaction with IPDI at the first stage, the reaction at the first stage proceeded rapidly at 100 ° C. and the reaction time was shorter than that in Example 6. To reach the desired conversion. Further, the reaction with the second stage T-80 proceeded rapidly at 40 ° C., which was lower than in Example 6. Using the resulting prepolymer, a waterproofing composition was prepared in the same manner as in Example 6. As a result, while exhibiting good coating film properties and ensuring sufficient pot life as a winter formulation, Construction of the process was possible. In the interlayer adhesion test, the adhesive strength was sufficient for practical use.

  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 weight

[23 ° C 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.

[23 ° C construction time (hours)]
In an air circulation type environmental test chamber at 23 ° C and 50% humidity, 2 kg / m ^{2 of} a waterproofing material in which the main agent and curing agent were stirred and mixed at a predetermined ratio was not completely cured. The time until it was possible to walk on the top with shoes and the work of the next process could be started was measured.

[Tensile strength (N / mm ² )]
A test piece having a curing condition of 23 ° C. for 7 days was measured based on JIS A 6021 (the tensile strength is 2.3 N / mm in the urethane rubber-based high elongation type (formerly Class 1) of JIS A 6021). ² or more).

[Elongation at break (%)]
Measurements were made based on JIS A 6021 for specimens with curing conditions of 7 days at 23 ° C. (JIS A 6021 urethane rubber high elongation type (formerly Class 1) has an elongation at break of 450% or more. ).

[Tear strength (N / mm)]
Measurements were made based on JIS A 6021 for test pieces with curing conditions of 7 days at 23 ° C. (in the case of urethane rubber high elongation type (formerly Class 1) of JIS A 6021, the tear strength is 14 N / mm or more) .

[Heat resistance Tensile strength ratio (%)]
About the test piece put into the 80 degreeC drying machine for 7 days and heat-processed, it carried out based on JISA6021 and calculated | required tensile strength ratio (%) with respect to a process.

[Tensile strength ratio after alkali treatment (%)]
Except for changing the treatment conditions to 60 ° C. for one week (23 ° C. for JIS A 6021), the tensile strength ratio (%) before treatment was determined based on JIS A 6021.

[Interlayer adhesion strength]
In a 23 ° C, 50% humidity air circulation environment test chamber, a primer is applied to a slate plate, dried for one day, and then a 2 kg / m ² waterproof material composition in which the main agent and curing agent are stirred and mixed at a predetermined ratio is applied. did. Three days later, 1 kg / m ^{2 of the} same waterproof material composition as that of the first layer was applied, covered with a sash as a reinforcing cloth, and further 1 kg / m ^{2 of the} same waterproof material composition was applied, and air at 23 ° C. and 50% humidity It was cured for 7 days in a circulation type environmental test chamber. After curing, the waterproof layer was cut into a width of 25 mm, and the interlayer adhesive strength (N / cm) of the first and second waterproof material compositions was measured by a 180 degree peel test (peel rate 100 mm / min).

[Primer adhesive strength]
In an air circulation type environmental test chamber at 23 ° C. and a humidity of 50%, OT primer M was applied to the slate plate, and OT primer A was applied to the top of 0.15 kg / m ² . After 3 days, base and curing agent agitating and mixing the waterproof material composition 1 kg / m ² was applied at a predetermined ratio, further covered with a bleached same waterproof material composition 1 kg / m ² applied as a reinforcing cloth thereon It was cured for 7 days in an air circulation type environmental test chamber at 23 ° C. and 50% humidity. After curing, the waterproof layer was cut to a width of 25 mm, and the adhesive strength (N / cm) between the primer A and the waterproof material composition was measured by a 180 degree peel test (peel speed 100 mm / min).

Claims (5)

  A two-pack type urethane waterproofing material composition comprising a main agent comprising an isocyanate group-terminated prepolymer comprising a polyisocyanate and a polyol and a curing agent comprising an aromatic polyamine and a plasticizer, the main agent comprising a tolylene diisocyanate skeleton and An isophorone diisocyanate skeleton is included in a molar ratio of 50/50 to 97/3, and the curing agent is 40/60 to 97 of diethyltoluenediamine and 4,4'-methylenebis (N-sec-butylaniline) as an aromatic polyamine. A two-component urethane waterproofing material composition comprising an equivalent ratio of / 3.   The two-component urethane waterproofing composition according to claim 1, wherein 80 equivalent% or more of the active hydrogen component in the curing agent is an aromatic polyamine.   The two-component urethane waterproof material composition according to claim 1 or 2, comprising an acid anhydride as a curing accelerator. A method for producing a two-component urethane waterproofing composition comprising a main component comprising an isocyanate group-terminated prepolymer comprising a polyisocyanate and a polyol and a curing agent comprising an aromatic polyamine and a plasticizer, the method comprising:
Tolylene diisocyanate, isophorone diisocyanate and polyol are reacted in the same vessel in a molar ratio of tolylene diisocyanate and isophorone diisocyanate in the range of 50/50 to 97/3 to give an isocyanate group-terminated prepolymer. Preparing a base comprising: and
Diethyltoluenediamine, 4,4′-methylenebis (N-sec-butylaniline) and a plasticizer are used, and the equivalent ratio of diethyltoluenediamine and 4,4′-methylenebis (N-sec-butylaniline) is 40/60 to 97. In the range of / 3, the method of mixing and preparing a hardening | curing agent is included.   The method according to claim 4, wherein the step of preparing the main agent includes a step of reacting isophorone diisocyanate and polyol in a container, and then a step of adding tolylene diisocyanate in the container and further reacting.