JP6839947B2 - Fast-curing two-component urethane waterproof material composition and its manufacturing method - Google Patents

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 waterproofing material is suitable for construction of irregular shapes and narrow parts and has excellent economic efficiency, so it is widely used for waterproofing balconies and eaves as well as rooftop waterproofing of concrete buildings, which is unique to Japan. Has achieved the development of.
The two-component urethane waterproofing material is constructed by mixing the two solutions of the main agent and the curing agent at the construction site with a stirrer for several minutes, and then applying them with a gold iron, comb spatula, rubber spatula, roller, brush, etc. The curing reaction starts at the same time as the start of mixing, the viscosity gradually increases, and after passing through a low viscosity state (hereinafter referred to as pot life) that is easy to install for a certain period of time, the viscosity becomes so high that it is difficult to install and cures. To go. It is said that the pot life is preferably at least about 30 minutes or more at the actual construction temperature, and for convenience, the time until the viscosity at 23 ° C. reaches 60,000 mPa · s is used as an index.

The longer the pot life is, the more preferable it is in the coating work, but in general, if the pot life is lengthened, the curability deteriorates, and the time until the worker can get on the coating film to carry out the next process (hereinafter, , It is called the workable time.) It also becomes long. In normal work, it is desired that the urethane waterproof material is applied in the evening and the work is ready for construction the next morning, and it is preferable that the workable time can be adjusted within about 17 hours throughout the year. ..
In summer construction, the temperature of the material rises to about 35 ° C and the reactivity increases. Therefore, in order to secure a pot life of 30 minutes, it is preferable that the pot life at 23 ° C is about 50 minutes or more. For that purpose, a suitable compounding technique is required. On the other hand, in winter, the material temperature drops to about 5 ° C and the reactivity decreases, so 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 so that it can be applied by the next morning, appropriate compounding technology is still required. Therefore, it is common to prepare at least two types of two-component urethane waterproofing materials, one for summer and the other for winter, to secure the pot life and the workable time according to each season.

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

Since the MOCA cross-linked waterproof material has mild reactivity, it is excellent in workability in summer when pot life is required, and it has relatively good mechanical strength, so it is still used as a general-purpose waterproof material. It is used. On the other hand, since MOCA cross-linked waterproofing material has poor curability at low temperature, it is common to add a large amount of lead carboxylate as an accelerator in winter, but there is a limit to the improvement of low temperature curability. Furthermore, there is a problem that heat deterioration is promoted by blending a large amount of lead compounds.
There is also a method of 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 is still a limit to improvement.

The MOCA crosslinked waterproof material also has a big environmental problem. MOCA used as a curing agent is designated as a Class 2 Specified Chemical Substance by the Industrial Safety and Health Act, and since it is used in a curing agent in excess of 1% of the upper limit, obstacles such as Specified Chemical Substances, etc. It will be a product that falls under the preventive rules (hereinafter referred to as specialization rules). In addition, MOCA is classified into Group 1 (carcinogenic to humans) in the carcinogenicity evaluation by IARC (International Agency for Research on Cancer).
In addition, the TDI used as the main agent is also designated as a specific chemical substance, and since the free TDI is present in the main agent of general-purpose products in excess of 1% of the upper limit, the main agent is also a product subject to the special rules. As a result, various restrictions are imposed during manufacturing and construction. Furthermore, lead carboxylate used as an accelerator is a material whose use is strictly restricted worldwide, and is designated as a specified type 1 designated chemical substance under the Chemical Substance Emission Control Promotion Law (commonly known as the Chemical Substances Control Law). It is a material that we want to avoid using from the environmental point of view.

In a two-component urethane waterproofing material, it is called a DETDA crosslinked waterproofing material using diethyltoluenediamine (hereinafter referred to as DETDA), which is more reactive than MOCA and has higher environmental safety with respect to TDI prepolymer. The type has also been commercialized. The DETDA cross-linked waterproof material has a feature of having good curability even at low temperatures, but it is necessary to add a large amount of plasticizer in order to secure the pot life in summer. However, if too much plasticizer is used, problems such as deterioration of adhesiveness to the top coat and increase of plasticizer migration will occur, so the amount used is limited and it is difficult to secure the pot life in the summer. There is.
As a method for securing the pot life of the DETDA crosslinked 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 are used. A method of using in combination with TDI (Patent Document 2), a method of using 4,4'-methylenebis (N-sec-butylaniline), which is a mildly reactive aromatic secondary amine, in combination with DETDA (Patent Document 3), etc. Although it has been proposed, there are still problems with each method, and it has not yet been generalized.

Since DETDA is considerably more reactive than water, a coating film containing DETDA as a main reaction component has an advantage that the foaming phenomenon can be suppressed even without lead carboxylate, which is further advantageous in terms of the environment. ..
Further, unlike the MOCA cross-linked waterproof material, the DETDA cross-linked waterproof material can further improve the curability by using a curing accelerator in winter, but the pot life is still shortened and the workability deteriorates. Will end up. Therefore, although a curing accelerator is not usually used, curing can be accelerated by a lead carboxylic acid compound such as lead 2-ethylhexanoate or a low molecular weight carboxylic acid such as 2-ethylhexanoic acid.
The curing accelerator is generally added to the curing agent side because it does not cause a problem in storage stability, but it is also added as a third component at the construction site. When adding at the construction site, there is the convenience that the amount of addition can be adjusted according to the temperature at the time of construction, but since the amount of addition is small, there is a problem that compounding mistakes are likely to occur and storage and management. There is also the problem that it is difficult.

As for the coating film performance of urethane waterproofing material, not only mechanical strength but also weather resistance, heat resistance, acid resistance, alkali resistance, etc. are specified in detail in JIS A 6021, and those satisfying this JIS standard. Otherwise, it will not be adopted by government offices, of course, and it will not be accepted as a product.

In addition, in the general urethane waterproofing method, a primer is applied to an inorganic base such as concrete to ensure adhesiveness, 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 concrete. For an inorganic base having a relatively large area, a ventilation buffer method is widely used in which various ventilation buffer sheets are applied, a urethane waterproof material is applied on the sheet, and then a top coat is applied.

In either method, the urethane waterproof layer is generally applied in two steps in order to compensate for defects in the coating film and ensure uniformity, and finally to a thickness of 2 mm to 3 mm. A simple method of applying a top coat after applying a urethane waterproof layer by 1 to 2 mm at a time is also widespread to some extent for construction sites such as balconies, eaves, and skirting boards.
At present, if one layer of urethane waterproofing material is applied, it will not cure during the day, so it is customary to perform the next process such as applying a second layer of urethane waterproofing material or applying a top coat the next day, and the construction period until completion. It is said that the drawback of urethane waterproofing material is that it becomes long. Furthermore, in recent years, climate change has tended to be severe, and there have been many problems that the uncured urethane waterproof layer is damaged by rainfall within a few hours after the urethane waterproof material is applied.

Japanese Patent No. 3114557 Japanese Patent No. 3957779 Japanese Patent No. 3445364

Recently, the shortage of construction workers has become remarkable, and the waterproofing industry also desires more efficient and labor-saving waterproofing methods and materials. In particular, urethane waterproofing materials require a construction period of 3 to 5 days even for construction of a small area, and there remains a big problem that the construction period is further significantly extended if the weather is unseasonable.
Furthermore, if it is expected to rain at night, urethane waterproofing material cannot be applied even if the weather is fine during the day, and because it was forcibly applied before the rain, the paint film was damaged by the rain. There is also the problem that a great deal of time and effort is spent on repairs.

Waterproofing materials that cure in about 5 hours after construction (can be constructed) and can be moved to the next process on the same day have been studied mainly for DETDA cross-linked waterproofing materials, 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 very small area or repair, and has not been generalized.
Further, the DETDA crosslinked waterproof material has a problem that the adhesiveness with the primer and the adhesiveness between the waterproof materials are not sufficient.
The general-purpose MOCA cross-linked waterproof material has the problems that the curability at low temperature deteriorates and the environmental compatibility is insufficient, and it can be cured all year round on the same day, and it is almost the same as the general-purpose waterproof material. A fast-curing urethane waterproof material that has the same pot life, has good adhesiveness and workability, and is environmentally friendly is desired.

When 4,4'-methylenebis (N-sec-butylaniline), which is an aromatic secondary amine that is milder in reactivity than DETDA, is used in combination with the DETDA cross-linked waterproof material, the pot life is not significantly impaired. However, by using 4,4'-methylenebis (N-sec-butylaniline), the heat resistance and alkali resistance are extremely reduced. Therefore, there is a problem that it is not practical.
On the other hand, it has been pointed out that, in the main agent, the pot life can be extended to some extent by using TDI and IPDI in combination, 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 the main agent, and DETDA and 4,4'-methylenebis in a specific range in the presence of a plasticizing agent as a curing agent. By using N-sec-butylaniline), it becomes quick-curing while maintaining the pot life, has excellent heat resistance and alkali resistance, and has good adhesion to primers and waterproof materials. , Found that it will be an environment-friendly fast-curing waterproof material. Further, the above composition is suitable for a fast-curing waterproof material for summer, which requires a pot life. However, by using an acid anhydride as a curing accelerator in this composition, the pot life can be used even at a low temperature. It was found that it is a fast-curing waterproof material that retains the above.

Further, in the method for producing the main agent, since the reaction rates of TDI and IPDI are significantly different in the prior art, a method of separately producing the TDI prepolymer and the IPDI prepolymer and blending the two is known (Patent Document 2). However, in the present invention, it is possible to carry out one-batch production in which TDI and IPDI are charged at the same time, or IPDI and polyol are charged first and the reaction is preceded to some extent, and then TDI is charged, which can greatly improve productivity. I understood.

The present invention includes the following aspects.
[1] A two-component urethane waterproofing composition composed of 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, and the main agent is tolylene diisocyanate. It contains a nat skeleton and an isophorone diisocyanate skeleton in a molar ratio of 50/50 to 97/3, and the curing agent contains diethyltoluenediamine and 4,4'-methylenebis (N-sec-butylaniline) as aromatic polyamines 40 /. A two-component urethane waterproof material composition containing an equivalent ratio of 60 to 97/3.
[2] The two-component urethane waterproof material 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 waterproof material composition according to [1] or [2], which contains an acid anhydride as a curing accelerator.
[4] A method for producing a two-component urethane waterproofing material composition, which comprises 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. Is
Tolylene diisocyanate, isophorone diisocyanate and polyol are reacted in the same container with a molar ratio of tolylene isocyanate to isophorone diisocyanate in the range of 50/50 to 97/3, and isocyanate group-terminated prepolymer. The process of preparing the main agent containing
The equivalent ratio of diethyltoluenediamine, 4,4'-methylenebis (N-sec-butylaniline) and plasticizer to diethyltoluenediamine and 4,4'-methylenebis (N-sec-butylaniline) is 40/60 to 97. A method comprising the step of mixing to prepare a curing agent in the range of 3/3.
[5] The step of preparing the main agent comprises a step of reacting isophorone diisocyanate and a polyol in a container, and then a step of adding tolylene diisocyanate into the container and further reacting the mixture, according to [4]. the method of.

The two-component urethane waterproof material composition of the present invention is a fast-curing waterproof material that retains a sufficient pot life in summer, and has excellent low-temperature curability even in winter while maintaining a pot life. It becomes a curable waterproof material, which makes it possible to shorten the construction period and improve the efficiency of construction throughout the year.
In addition, it is an environment-friendly quick-curing urethane waterproof material with good productivity, good heat resistance and alkali resistance, excellent adhesion to primers and adhesiveness between waterproof materials.

Generally, it is desirable that the usable time of the waterproof material for summer is 50 minutes or more in the measurement at 23 ° C., and the workable time is preferably about 20 hours at 23 ° C., MOCA. Cross-linked waterproofing materials are relatively easy to meet this goal.
On the other hand, the DETDA crosslinked waterproof material exhibits a quick curing property with a workable time of about 5 to 7 hours, but it is difficult to set the pot life to 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 agent polyisocyanate, the pot life is increased. It becomes difficult to secure. A special product called T-100, which contains 100% of 2,4-TDI, is advantageous for securing pot life, but the supply amount is limited, so it can be used as a raw material for a versatile waterproof material. Is not suitable.

The pot life can be extended to some extent by using the TDI prepolymer and the IPDI prepolymer in combination as the main agent isocyanate group-terminated prepolymer (Patent Document 2), but this method reduces curability and physical properties. It has been pointed out that there is a decrease, and there is also a problem that the productivity is decreased because it is necessary to blend and produce two kinds of prepolymers.

For one curing agent, the combined use of 4,4'-methylenebis (N-sec-butylaniline), which is a low-reactive aromatic secondary amine, with DETDA is an effective method for extending the pot life ( Patent Document 3) Moreover, since the combined use of 4,4'-methylenebis (N-sec-butylaniline) in a certain range shows the property that the curability is not significantly impaired, the pot life is extended without significantly impairing the fast curability. Can be made possible. However, the use of 4,4'-methylenebis (N-sec-butylaniline) causes a big practical problem that the heat resistance and the alkali resistance are extremely lowered at the same time as the physical characteristics are lowered.

As a result of conducting a detailed study on the DETDA crosslinked waterproof material again, the present invention also refers to a tolylene diisocyanate skeleton (hereinafter, also referred to as “TDI skeleton”) and an isophorone diisocyanate skeleton (hereinafter, also referred to as “IPDI skeleton”). As a summer waterproofing material by using a main agent containing () in a specific range and using DETDA and 4,4'-methylenebis (N-sec-butylaniline) as an aromatic polyamine component of the curing agent in a specific range. , We have found that it is a fast-curing waterproof material that can secure the pot life more than before.

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 represented by the formula (1).

The IPDI skeleton refers to the molecular structure represented by the 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) as the curing agent at the same time, but at the same time, 4,4'. It was found that the heat resistance and alkali resistance, which are the biggest problems in using -methylenebis (N-sec-butylaniline), tend to improve.
In addition, although the curability tends to be delayed by the combined use of IPDI, the fast-curing property, which is a characteristic of the DETDA cross-linked type, is maintained, so that it becomes a fast-curing waterproof material that retains its pot life in summer. If the temperature is around 30 ° C, the construction can be done in about 5 hours, and two processes can be performed a day.
Further, by using IPDI in combination with the main agent, the adhesiveness with the primer and the adhesiveness between the waterproof materials can be improved, and in this respect as well, the weak points of the DETDA crosslinked waterproof material can be improved.

(Main agent)
In the present invention, the main agent needs to contain the TDI skeleton and the 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 is more than 50, it is difficult to become a fast-curing waterproof material, and if it is less than 3, it becomes a fast-curing waterproof material with good heat resistance and alkali resistance that secures pot life. hard.

(Polyisocyanate)
Polyisocyanates for introducing a TDI skeleton into the main agent include T-65, which has an equivalent ratio of 2,4-TDI and 2,6-TDI, which is commercially available, 65/35, and T-65, which is 80/20. T-100, which is -80 and 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, there is a limit to the production amount. Although T-100 is advantageous in terms of securing pot life, it is preferable to use T-80 as a main component in order to use it as a versatile urethane waterproof material. In addition, derivatives such as a dimer form, a nurate form, and an allophanate form of TDI can be used in some cases. Preferably, all of the TDI backbone is derived from the TDI monomer.

As the polyisocyanate for introducing the IPDI skeleton into the main agent, IPDI monomers, nurates, adducts, allophanates and other IPDI derivatives can be used. Preferably, the IPDI backbone is derived from the IPDI monomer.

In the present invention, an IPDI monomer or an IPDI derivative can be added to the TDI prepolymer, but the effect of improving the adhesiveness with the primer and the adhesiveness between the waterproofing materials and the effect of prolonging the pot life are described in TDI. And it is effective to use IPDI as a prepolymer. Therefore, it is preferable that TDI and IPDI are used as prepolymers as the main agent of the present invention.

Further, although some other polyisocyanates can be used in combination, the isocyanate group is preferably less than 30 equivalent%, more preferably less than 20 equivalent%, and less than 10 equivalent%. Is even more preferable. If the amount of other polyisocyanates is 30 equivalents or more, it is difficult to obtain a fast-curing waterproof material having a pot life. Other polyisocyanates include hexamethylene diisocyanate, norbornene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, water-added diphenylmethane diisocyanate, and water-added tetramethylxylylene diisocyanate. Examples thereof include less reactive polyisocyanates such as, and relatively highly reactive polyisocyanates 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 becomes difficult to secure the pot life.

(Polyprethane used as the main agent)
As the polyol used as the main agent, the polyol usually used as the main agent of the urethane waterproof material can be used, but in order to make the main agent having low viscosity and good workability, a polyoxypropylene polyol having a molecular weight of 300 to 8000 or poly is used. It is preferable to use a polyether polyol such as an oxyethylene polyoxypropylene polyol. In addition, other high molecular weight polyols such as polyester can be used as long as they are a part.
Further, 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.

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

(Main agent NCO group / OH group equivalent ratio)
It is preferable to mix the polyisocyanate and the polyol so that the equivalent ratio of the NCO group to the OH group of the main agent and the NCO group / OH group are 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 is difficult to obtain a waterproof material with good physical characteristics. If the number exceeds 2.3, the amount of free TDI or IPDI increases, making it difficult to secure the pot life.
Further, it is more preferable to set the NCO group / OH group to 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 also be an environment-friendly waterproof material.

(Manufacturing method of main agent)
Due to the large difference in reactivity between TDI and IPDI, it is common to manufacture TDI prepolymers and IPDI prepolymers separately and blend them together in a "mixing" method, which provides adhesion to primers and waterproofing materials. It has a high effect of improving the adhesiveness of the polymer, has an effect of extending the pot life, and can also confirm the effect of improving the heat resistance and the alkali resistance. However, this method requires a lot of production equipment and time because it requires two separate synthesis steps and a further blending step, which impairs economic efficiency.

As a result of further studies, it was found that batch production using the same reaction vessel is possible. First, in the "batch preparation" method in which TDI and IPDI are charged almost at the same time, for example, when a reaction is carried out at around 100 ° C., some of the low-reactivity IPDI also reacts, probably because the IPDI monomer is produced after the production of the TDI prepolymer. Compared with the method of adding, the effect of extending the pot life and the effect of improving the adhesiveness between the primers or waterproofing materials were clarified, and the heat resistance and alkali resistance were also improved. However, when the remaining amount of the monomer of IPDI increases, it tends to be difficult to secure the pot life and the physical properties.

Next, a "two-stage preparation" method in which IPDI was charged first and the reaction with the polyol was preceded to some extent and then TDI was charged was examined. Since the reaction between the IPDI and the polyol in the first stage has a large excess of hydroxyl groups, for example, at a reaction temperature of 100 ° C. without a catalyst, about 50% of all the isocyanate groups of the IPDI reacted in about 8 to 10 hours. By this method, the IPDI monomer can be reduced. Moreover, the polyol can also be blended separately. After that, when TDI is charged as the second step and the reaction is started at, for example, 100 ° C., it seems that the isocyanate group of TDI, which is more reactive than IPDI, reacts preferentially with the polyol, and after a few hours, the target NCO content Can be reacted up to. In this method, it seems that a considerable amount of secondary isocyanate groups of IPDI, which is finally low in reactivity, remains, and the pot life extension effect and the primer or waterproof material are almost the same as those of the conventional "mixing" method. It was found that the effect of improving the adhesiveness between the two 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 IPDI and the polyol in the first stage. Moreover, it was found that the reaction rate of the first stage could 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, and in particular, dioctyltin dilaurate and dibutyltin dilaurate, which are organic quaternary tin compounds, can be used. The reaction time of the first stage can be shortened, and the reaction can be rapidly advanced even at a low temperature of about 60 ° C. The amount of organic ditin 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 of the first stage reaches an arbitrary reaction rate, the reaction can be almost stopped by adding a material for deactivating the urethanization catalyst such as phosphoric acid, and moreover, the inactivating agent of this inactivating agent. The addition has the effect of preventing a runaway reaction due to a side reaction such as allophanation during the reaction with the second-stage TDI, and the reaction can proceed safely and smoothly.
Examples of the deactivator of the urethanization catalyst include inorganic acids and chlorine-based acidic substances such as benzoyl chloride and phthalate chloride, and among them, phosphoric acid is preferable because it is effective. The amount of phosphoric acid used varies depending 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 all the 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 will eventually remain, so that the effect of extending the pot life and the effect of improving the adhesiveness will be insufficient. Since the number of monomer groups is reduced, the effect of extending the pot life, the effect of improving the adhesiveness, and the effect of improving the heat resistance and the alkali resistance are insufficient.
The above-mentioned "two-stage preparation" method is more effective than the "batch preparation" method in which TDI and IPDI are charged at the same time, and is more effective in securing the pot life, improving the adhesiveness with the primer and the adhesiveness between the waterproof materials, and has heat resistance and resistance. Since the alkalinity is also good, it is a more preferable production method in the present invention.

(Main agent NCO / curing agent NH ₂ equivalent ratio)
The equivalent ratio of the isocyanate group of the main agent to the amino group of the aromatic polyamine of the curing agent, that is, the main agent NCO / curing agent NH ₂ is preferably 0.9 to 1.8. If the main agent NCO / curing agent NH ₂ at the time of mixing the two liquids is less than 0.9, the molecular weight is insufficient and the physical properties are deteriorated. If it exceeds 1.8, the curability is lowered and the physical properties are also insufficient.

(Curing agent active hydrogen compound)
The present application should contain DETDA and 4,4'-methylenebis (N-sec-butylaniline) as aromatic polyamines in an equivalent ratio of 40/60 to 97/3, of 50/50 to 95/5. The range is preferable, and the range is more preferably 60/40 to 90/10. If the equivalent ratio of 4,4'-methylenebis (N-sec-butylaniline) to DETDA exceeds 60, it will not be fast-curing, and at the same time it will be difficult to maintain physical properties and heat resistance / alkali resistance. The effect of extending the pot life becomes insufficient.
Although isomers such as 3,5-diethyl-2,4-toluenediamine and 3,5-diethyl-2,6-toluenediamine are present in DETDA, any isomer may be used in the present application. Well, or a mixture 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 Corporation can be obtained. As 4,4'-methylenebis (N-sec-butylaniline), EtaCure 420 manufactured by Albemarle Corporation can be obtained.

Further, 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). , 20 equivalent% or less is more preferable. When the amount of other aromatic polyamines exceeds 30 equivalents, it is difficult to obtain a fast-curing waterproof material that retains 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 has high reactivity similar to 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 it is often highly crystalline or poorly soluble. It is preferably less than 30 equivalent% in the aromatic polyamine.

As low-reactivity aromatic polyamines, EtaCure 300 (dimethylthiotoluenediamine) manufactured by Albemar, Erasmer 650P (polytetramethylene glycolbis (p-aminobenzoate)) manufactured by Ihara Chemical Co., Ltd., and Ihara Chemical Co., Ltd. Porea SL-100A (poly (tetramethylene / 3-methyltetramethylene ether) glycolbis (4-aminobenzoate)) manufactured by Polea SL-100A, etc., can be mentioned, but as the amount used increases, the quick-curing property tends to be impaired. It is also preferable that the content is less than 30 equivalent% in the aromatic polyamine.

In the present application, 80 equivalent% or more of the active hydrogen component in the curing agent is preferably an aromatic polyamine, and more preferably 90 equivalent% or more. If the amount of other active hydrogen components exceeds 20 equivalent%, sufficient pot life and quick curing cannot be obtained.

If the amount of the polyol as the active hydrogen component in the curing agent is 20 equivalent% or less, it can be used for adjusting the pot life, adjusting the viscosity, adjusting the wetness, adjusting the physical properties, improving the adhesiveness, and the like.
Examples of the polyols 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 pentadiol, trimethylolpropane and glycerin can also be used.

(Plasticizer)
It is necessary to use a plasticizer to secure the pot life time, and it is preferable to use 20 to 90 parts by mass of the plasticizer with respect to 100 parts by mass of the prepolymer in the main agent, and 25 to 80 parts by mass. It is more preferable to use the part. It is not possible to secure pot life without using a plasticizer. The plasticizer is preferably blended with the curing agent, but it can also be partially blended with the main agent side.

As the plasticizer, a plasticizer that can be generally blended with urethane resin can be used. For example, phthalates such as diisononyl phthalate (DINP), dioctyl phthalate (DOP), butyl benzyl phthalate (BBP), aliphatic dibasic acid esters, phosphoric acid esters, trimellitic acid esters, etc. Examples thereof include sebacic acid esters, epoxy fatty acid esters, glycol esters, animal and vegetable oil-based fatty acid esters, petroleum / mineral oil-based plasticizers, and alkylene oxide polymerization-based plasticizers. Among them, diisononyl phthalate (DINP) and dioctyl phthalate (DOP), which have a flash point of 200 ° C. or higher, are less likely to cause weight loss in the long term, and are aromatic polyesters and are less likely to cause hydrolysis, and are therefore preferably used. 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 a physical property conforming to JIS standards, and an economical waterproof material can be obtained. The filler is preferably blended in the curing agent, but can also be partially blended on the main agent side. The blending amount of the inorganic filler is preferably 20 parts by mass to 80 parts by mass in the curing agent. If the amount of 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 resin content is reduced, so that the physical properties are likely to be lowered and the viscosity is likely to be increased.

Examples of the filler include calcium carbonate, which has good dispersibility during production, can easily maintain a relatively low viscosity state even when the blending amount is increased, and has a high cost reduction effect. Examples of calcium carbonate include heavy calcium carbonate, light calcium carbonate, colloidal calcium carbonate, and various surface-treated calcium carbonates, and any of these calcium carbonates can be used. Further, since appropriate shaking denaturation can be obtained by blending the surface-treated colloidal calcium carbonate, it is also possible to manufacture a waterproof material for elevation. As other inorganic fillers, silica-based, kaolin-based, talc-based, bentonite-based, etc. can be used, but as the amount used increases, the viscosity becomes severe and it is difficult to control the water content. It is preferable that calcium carbonate is the main component. In addition, some organic fillers can be used.

Although a solvent can be used in the curing agent, there is a risk of shrinkage due to volatilization after construction, there is a tendency for the inorganic filler to settle easily, and there are environmental problems, so 5% by mass. It is preferable to use within, and it is more preferable not to use it. 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 waterproofing material of the present application is suitable not only for leveling waterproofing materials for flat fields, but also for elevational waterproofing materials having non-sagging properties and can be applied to elevations and slopes. The waterproof material for elevation contains a large amount of non-sag property-imparting agent such as surface-treated colloidal calcium carbonate, and requires a longer pot life than the waterproof material for flat ground to construct complicated parts. It is possible to cope with this more sufficiently, and it is also possible to exhibit quick curing.

As a result, even in the summer when the temperature is around 30 ° C, it is possible to make a fast-curing waterproof material that has a pot life of 30 minutes or more and enables the next process in about 5 hours, and has heat resistance and resistance. At the same time as having good alkalinity, it is possible to improve the adhesiveness with the primer and the adhesiveness between the waterproof materials. The general-purpose MOCA cross-linked waterproof material for summer can be used for 30 minutes or more at 30 ° C, and the part exposed to direct sunlight can be installed in about 5 hours, but the shaded part. In many cases, the workable time is about 7 to 10 hours, and it is difficult to achieve the fast curing property of the present application, so that it is difficult to perform two steps a day.

(Curing accelerator)
Next, a detailed study was conducted on the use of the fast-curing waterproof material that secured the above-mentioned pot life throughout the year. The conventional DETDA cross-linked waterproof material has relatively good low-temperature curability, but if it is attempted to be able to be applied in about 5 hours at a low temperature of about 10 ° C, the pot life will be 30 minutes or less, and the work will be done. The sex gets worse. 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 amount of plasticizer, a carboxylic acid metal salt such as lead 2-ethylhexanoate as an accelerator, or Examples thereof include a method using a carboxylic acid such as 2-ethylhexanoic acid, but both methods significantly shorten the pot life.

However, as a result of examining various possibilities, when an acid anhydride is used as a curing accelerator for the composition of the present invention, it plays a role of promoting curing without shortening the pot life so much, and even at a low temperature. It was found to show fast curing.
It is considered that the acid anhydride generates a carboxylic acid group by an addition reaction with an amino group such as DETDA in a curing agent, a hydroxyl group of a polyol, and an active hydrogen group such as water, and exhibits a curing promoting action. At that time, the addition reaction between the acid anhydride and the active hydrogen group is not instantaneous and seems to have an appropriate reaction rate, and as a result, the carboxylic acid group gradually increases, so that it can be used for several tens of minutes. Although the effect on time is small, it is presumed that it acts effectively on the curability after several hours and exerts a potential accelerator effect.

The present invention uses a conventional curing accelerator as a low molecular weight carboxylic acid such as 2-ethylhexanoic acid or a metal carboxylic acid salt such as zinc 2-ethylhexanoate or lead 2-ethylhexanoate as a curing accelerator. However, it is preferable to use an acid anhydride as a curing accelerator, which can exhibit faster curing property after securing a pot life than a conventional accelerator. The acid anhydride can also be used as a waterproof material for summer, and although the pot life is slightly shortened, it can be used as a quick-curing waterproof material with good workability in spring and autumn.

The acid anhydride can be added to the curing agent side in advance, but in that case, it reacts with the active hydrogen group in the curing agent over time to generate a carboxylic acid group, so that the conventional 2-ethylhexane is used. It has the same effect as acid and shortens the pot life. Therefore, in the present application, the method of adding the acid anhydride to the main agent or when mixing the main agent and the 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 containing an isocyanate group-terminated prepolymer, a curing agent part containing an aromatic polyamine and a plasticizing agent, and a curing including an acid anhydride are used. An example of how to prepare a kit consisting of accelerator parts and mix those parts at the construction site can be illustrated.
When an acid anhydride is added to the main agent, the acid anhydride can be kept in a stable state because the main agent does not have an active hydrogen group, and the addition reaction of the acid anhydride is started by mixing with the curing agent. It can exert its effect as a potential accelerator. Further, when the third component is added when the main agent and the curing agent are mixed at the construction site, complicated work such as subdivision and light weight is involved, so it is more preferable to add an acid anhydride to the main agent.

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 bisamhydrotrimethylate, glycerin bisamhydrotrimerite 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-3-3) Furanyl) naphtho [1,2-c] furan-1,3-dione, 1,2,3,4-butanetetracarboxylic anhydride dianhydride and the like can be mentioned.
The acid anhydride may be used alone or in combination of two or more.

Since the two-component urethane waterproof material is applied by mixing the main agent and the curing agent at the construction site, the acid anhydride solid at room temperature may not be completely dissolved in the mixed solution and may crystallize. When the acid anhydride is crystallized, a sufficient curing promoting effect may not be obtained. Therefore, an acid anhydride that is liquid at room temperature is preferable. Examples of the acid anhydride liquid at room temperature include phthalic anhydride, propionic anhydride, succinic anhydride, and HN-2200 (3-methyl-1,2,3,6-tetrahydrophthalic anhydride manufactured by Hitachi Kasei Co., Ltd.). 4-Methyl-1,2,3,6-tetrahydrophthalic anhydride mixture), Ricacid HH (hexahydrophthalic anhydride) manufactured by Shinnihon Rika Co., Ltd., Ricacid MH-700 (3-) manufactured by Shinnihon Rika Co., Ltd. Methylhexahydrophthalic anhydride / 4-methylhexahydrophthalic anhydride = 70/30 mixture), Ricacid MH (4-methylhexahydrophthalic anhydride) manufactured by Shinnihon Rika Co., Ltd., manufactured by Shinnihon Rika Co., Ltd. Ricacid HNA-100 (mixture of methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride and bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride), Hitachi Chemical Co., Ltd. MHAC-P (methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride) manufactured by the company, DSA (tetrapropenylphthalic anhydride) manufactured by Sanyo Kasei Kogyo Co., Ltd., Shin Nihon Rika Co., Ltd. The company's Ricacid OSA (octenyl succinic anhydride) is mentioned, and among them, HN-2200 (3-methyl-1,2,3,6-tetrahydrophthalic anhydride and 4-methyl-) manufactured by Hitachi Kasei Co., Ltd. 1,2,3,6-tetrahydrophthalic anhydride mixture), MHAC-P (methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride) manufactured by Hitachi Kasei Co., Ltd., new Ricacid MH-700 (3-methylhexahydrophthalic anhydride / 4-methylhexahydrophthalic anhydride = 70/30 mixture) manufactured by Nippon Rika Co., Ltd., DSA (tetrapropenylphthalic anhydride) manufactured by Sanyo Kasei Kogyo Co., Ltd. ) Etc. are more preferable.

The amount of the acid anhydride used is preferably 0.05 to 10.0 g with respect to 100 g of the main agent, and more preferably 0.1 to 5.0 g. If the amount of acid anhydride used is too small, sufficient quick-curing property cannot be obtained, while if it is too large, sufficient pot life cannot be secured and the physical properties deteriorate.

In the present invention, it is preferable to use an acid anhydride as a curing accelerator, but other curing accelerators can be used, and they can also be used in combination with an acid anhydride.
Examples of other curing accelerators include organic stannic compounds, tertiary amines, metal carboxylic acid salts, and carboxylic acids. Examples of the organic ditin-based compound include dibutyltin oxide, dioctyltin oxide, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin di2-ethylhexanoate, dioctyltin diacetate, dioctyltin dilaurate, dibutyltin dimercaptide, and dibutyl. Examples thereof include tin bisacetylacetonate, dibutyltin oxylaurate, dioctyltin dineodecanate, dibutyltin bisbutylmalate and dioctyltin 2-ethylhexylmalate, and among them, dibutyltin dilaurate and dioctyltin dilaurate are preferable. It is preferable to use 0.001 to 0.1% by mass of the organic stannic compound in the curing agent.

As the tertiary amine, for example, general tertiary amines such as triethylamine, tributylamine, triethylenediamine, N-ethylmorpholine, bis (2-morpholinoethyl) ether, and diazabicycloundecene can be used. , A imidazole compound which is a special tertiary amine is preferable, and examples of the imidazole compound include 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-benzyl-2-methylimidazole and 1-benzyl-2-. Compounds having substituents at the 1- and 2-positions such as phenylimidazole and compounds having substituents at the 1-position such as 1-methylimidazole and 1-allyl imidazole can be used. Of these, imidazole compounds having substituents at the 1- and 2-positions are preferable. The tertiary amine is preferably used in an amount of 0.01 to 2.0% by mass in the curing agent.

In addition, a metal carboxylic acid salt, which is generally a urethane curing accelerator, can also be used. Examples of the carboxylic acid metal salt include 2-ethylhexanoic acid, neodecanoic acid, naphthenic acid, oleic acid, linoleic acid, linolenic acid, lead salt of resin acid, zinc salt, bismuth salt, zirzyl zyl salt, tin salt and copper salt. , Magnesium salt, calcium salt, strontium salt, barium salt and the like, and it is preferable to use 0.1 to 4.0% by mass of the carboxylate metal salt 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, and 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 blended on 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, if necessary.

Raw materials The raw materials used in the following examples and comparative examples are as follows.
[Isocyanate]
IPDI: VESTANAT® IPDI, isophorone diisocyanate alone, NCO content 37.8% by mass, NCO functional group number about 2.0, Ebonic Japan Co., Ltd. T-80: Coronate T-80, 2, 4 -Trirange isocyanate / 2,6-Trirange isocyanate = 80/20 (mass ratio) mixture, NCO content 48.3% by mass, manufactured by Nippon Polyurethane Industry Co., Ltd. [Polyprethane]
Sanniks PP-2000: Polyoxypropylene diol, average molecular weight 2000, OH value 56.1 mgKOH / g, Sanyo Kasei Kogyo Co., Ltd. Sanniks GH-3000: Polyoxypropylene triol, average molecular weight 3000, OH value: 56.1 mgKOH / G, manufactured by Sanyo Kasei Kogyo Co., 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 Corporation [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 Co., Ltd. HN- 2200: 3- or 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, manufactured by Hitachi Kasei Co., Ltd. [Plasticizer]
DINP: Sansosizer DINP, Diisononyl phthalate, manufactured by New Japan Chemical Co., Ltd. [Inorganic filler]
Calcium carbonate NS # 100: NS # 100, calcium carbonate, manufactured by Nitto Flour Chemical Co., Ltd. [Additives]
Additives: Kusumoto Kasei Co., Ltd. [Primer]
OT Primer M: 1-component moisture-curable mediator primer, manufactured by Tajima Roofing Co., Ltd. OT Primer A: 1-component moisture-curable primer, manufactured by Tajima Roofing Co., Ltd.

Preparation of main agent [Two-stage preparation] Method The polyol and solvent, IPDI and, if necessary, a catalyst were charged into a four-necked flask according to the formulations shown in Tables 1 to 5. Then, the reaction was carried out at a predetermined temperature for a predetermined time with stirring, and after the reaction was completed, phosphoric acid was added as needed. Further, T-80 was charged and reacted again at a predetermined temperature for a predetermined time to obtain a prepolymer.
[Batch preparation] Method The polyol, solvent, and polyisocyanates were charged into a four-necked flask according to the formulation shown in Table 4. Then, 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, the four-necked flask was charged with the polyol and solvent, IPDI and, if necessary, a catalyst. Then, 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. The IPDI prepolymer and the T-80 prepolymer were mixed in a predetermined ratio and used as the main agent.
In addition, each prepolymer was used as a main agent by adding a plasticizer, a catalyst and the like as needed.

Preparation of curing agent According to the formulation shown in Tables 1 to 5, liquids are charged in a metal container, mixed at a low speed with a stirrer (dissolver blade) to make them uniform, and then calcium carbonate is added and mixed at 1500 rpm for 15 minutes to mix each curing agent. Obtained.

Examples 1 and 2 (Table 1)
This is an example of a summer formulation using IPDI and T-80 as polyisocyanates, a main agent synthesized by the "two-stage preparation" method, and a curing agent with an equivalent ratio of DETDA and EtaCure 420 of 70/30. .. Example 1 in which the equivalent ratio of IPDI to T-80 is 20/80 shows good coating film physical properties as a waterproof material and secures sufficient pot life as a summer compound, while the next process is carried out during the day. It was possible. In the interlayer adhesion test, the interlayer adhesion strength was so strong that urethane material fracture occurred without delamination. Moreover, in the adhesion test with the primer, the adhesive strength was sufficient for practical use. In Example 2 in which the equivalent ratio of IPDI to T-80 was 10/90, the next step could be carried out within the day while showing good coating film physical properties as a waterproof material and ensuring sufficient pot life. .. In addition, the interlayer adhesion test and the primer adhesion test showed sufficient adhesive strength for practical use.

Comparative Example 1 (Table 1)
This is an example of a summer formulation in which only T-80 is used as the main polyisocyanate with respect to the curing agent having the same composition as in Examples 1 and 2. The pot life was 45 minutes, which was insufficient for the summer formulation. The interlayer adhesive strength and primer adhesive strength were lower than those of Examples 1 and 2, and it was considered that there was a problem in practical use. In addition, the tensile strength ratio after the heat treatment or the alkali treatment tended to be lower than that in Examples 1 and 2. In particular, the tensile strength ratio after the alkali treatment was as low as 71%, which seemed to be a problem in practical use.

Examples 3 and 4 (Table 2)
This is an example of a summer formulation using IPDI and T-80 as polyisocyanates, a main agent synthesized by the "two-stage preparation" method, and a curing agent with an equivalent ratio of DETDA and EtaCure 420 of 60/40. .. Examples 3 and 4 in which the equivalent ratios of IPDI and T-80 are 20/80 and 10/90, respectively, show good coating film physical properties as a waterproof material and secure sufficient pot life as a summer formulation on the day. It was possible to construct the next process inside. Moreover, in the interlayer adhesion test, the adhesive strength was sufficient for practical use.

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

Examples 5, 6 and 7 (Table 3)
IPDI and T-80 are used as polyisocyanates, and 1.00% by mass of acid anhydride catalyst HN-2200 is added to the prepolymer synthesized by the "two-stage preparation" method, and the equivalent ratio of DETDA and EtaCure 420. This is an example of a winter formulation using a curing agent having a value of 80/20. Examples 5, 6 and 7 in which the equivalent ratios of IPDI and T-80 are 30/70, 20/80 and 10/90, respectively, show good coating film physical properties as a waterproof material and have a sufficient pot life as a winter formulation. It was possible to carry out the construction of the next process within the day while ensuring the above. Moreover, in the interlayer adhesion test, the adhesive strength was sufficient for practical use.

Comparative Example 3 (Table 3)
This is an example of a winter formulation in which only T-80 is used as the main polyisocyanate with respect to the curing agent having the same composition as in Examples 5, 6 and 7. The pot life was 24 minutes, which was insufficient for winter formulation. The interlayer adhesive strength was lower than that of Examples 5, 6 and 7, and it was considered that there was a problem in practical use. In addition, the tensile strength ratio after the heat treatment or the alkali treatment tended to be lower than that in Examples 5, 6 and 7.

Example 8 (Table 4)
This is an example of a winter formulation in which the main agent having the same composition as in Example 7 is synthesized by the “bulk preparation” method. In Example 8, the next step could be carried out within the same day while exhibiting good coating film physical properties as a waterproof material and ensuring sufficient pot life as a winter compound. Moreover, in the interlayer adhesion test, the adhesive strength was sufficient for practical use.

Example 9 (Table 4)
An example of a winter formulation using an IPDI prepolymer and a T-80 prepolymer that were separately synthesized and "mixed" so that the equivalent ratio of IPDI to T-80 was 10/90, the same as in Example 7. is there. In Example 9, the next step could be carried out within the same day while exhibiting good coating film physical properties as a waterproof material and ensuring sufficient pot life as a winter compound. Moreover, in the interlayer adhesion test, the adhesive strength was sufficient for practical use.

Examples 10, 11, 12 (Table 5)
This is an example of a winter formulation using a catalyst when synthesizing a prepolymer by the "two-stage preparation" method with the same formulation as in Example 6. 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. Then, after adding 0.0015% by mass of phosphoric acid to inactivate the catalyst, a reaction with T-80 in the second stage was carried out, and the reaction proceeded rapidly at 100 ° C. When the waterproof material composition was prepared in the same manner as in Example 6 using the obtained prepolymer, the following was performed during the day while showing good coating film physical properties and ensuring sufficient pot life as a winter formulation. It was possible to construct the process. Moreover, 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. to a desired conversion rate in a shorter reaction time than in Example 6. Reached. Furthermore, the reaction with T-80 in the second stage also proceeded rapidly at 100 ° C. When the waterproof material composition was prepared in the same manner as in Example 6 using the obtained prepolymer, the following was performed during the day while showing good coating film physical properties and ensuring sufficient pot life as a winter formulation. It was possible to construct the process. Moreover, 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 in the first stage, the reaction in the first stage proceeded rapidly at 100 ° C. and the reaction time was shorter than that in Example 6. The desired conversion rate was reached. Furthermore, the reaction with T-80 in the second stage proceeded rapidly at 40 ° C., which was lower than in Example 6. When the waterproof material composition was prepared in the same manner as in Example 6 using the obtained prepolymer, the following was performed during the day while showing good coating film physical properties and ensuring sufficient pot life as a winter formulation. It was possible to construct the process. Moreover, in the interlayer adhesion test, the adhesive strength was sufficient for practical use.

The measurement method for 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 0.5 N-n-butylamine (toluene solution), 10 mL of toluene and an appropriate amount of bromphenol blue are added thereto, and then about 100 mL of methanol is added to dissolve the mixture. The mixture is titrated with a 0.25N hydrochloric acid solution. NCO (mass%) is calculated by the following formula.
NCO (mass%) = (blank titration value-0.5N hydrochloric acid solution titration value) x 4.202 x 0.25N hydrochloric acid solution factor x 0.25 / sample weight

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

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

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

[Elongation rate at break (%)]
The test piece whose curing condition was 23 ° C. for 7 days was measured based on JIS A 6021 (the urethane rubber-based high elongation type (former class 1) of JIS A 6021 has an elongation rate of 450% or more at break. ).

[Tear strength (N / mm)]
The test piece whose curing condition was 23 ° C. for 7 days was measured based on JIS A 6021 (the tear strength of the urethane rubber-based high elongation type (former class 1) of JIS A 6021 is 14 N / mm or more). ..

[Heat resistance Tensile strength ratio (%)]
The test piece heat-treated in a dryer at 80 ° C. for 7 days was subjected to JIS A 6021 to determine the tensile strength ratio (%) with respect to that before the treatment.

[Tensile strength ratio (%) after alkali treatment]
Except for changing the treatment conditions to 60 ° C. for 1 week (23 ° C. in JIS A 6021), the treatment was carried out based on JIS A 6021, and the tensile strength ratio (%) with respect to that before the treatment was determined.

[Interlayer adhesive strength]
In an air circulation type environmental test room at 23 ° C. and 50% humidity, a primer is applied to the slate plate, dried for one day, and then 2 kg / m ^{2 of} the waterproof material composition in which the main agent and the curing agent are stirred and mixed at a predetermined ratio is applied. did. After 3 days, the first layer the same waterproof material composition 1 kg / m ² was coated with a further covered with bleached same waterproof material composition 1 kg / m ² was applied as a reinforcing cloth thereon, 23 ° C., humidity of 50% air It was cured for 7 days in a circulating environment test room. After curing, the waterproof layer was cut to a width of 25 mm, and the interlayer adhesion strength (N / cm) between the first layer and the second layer of the waterproof material composition was measured by a 180-degree peeling test (peeling speed 100 mm / min).

[Primer adhesion strength]
In an air circulation type environmental test room at 23 ° C. and 50% humidity, OT primer M was applied to a slate plate, and 0.15 kg / m ² of OT primer A was applied thereto. ^{After 3 days, apply 1 kg / m 2 of} the waterproof material composition in which the main agent and the curing agent are stirred and mixed at a predetermined ratio, cover it with air as a reinforcing cloth, and further apply ^{1 kg / m 2 of the same waterproof material composition.} It was cured for 7 days in an air circulation type environmental test room 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 peeling test (peel speed 100 mm / min).

Claims (5)

A two-component urethane waterproofing composition composed of a main agent containing an isocyanate group-terminated prepolymer composed of polyisocyanate and a polyol and a curing agent containing an aromatic polyamine and a plasticizing agent, and the main agent is a tolylene diisocyanate skeleton. It contains an isophorone diisocyanate skeleton in a molar ratio of 50/50 to 97/3, and the curing agent is diethyltoluenediamine and 4,4'-methylenebis (N-sec-butylaniline) as aromatic polyamines 40/60 to 97. A two-component urethane waterproofing material composition containing an equivalent ratio of / 3. The two-component urethane waterproof material 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, which contains an acid anhydride as a curing accelerator. A method for producing a two-component urethane waterproofing material composition, which comprises 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.
Tolylene diisocyanate, isophorone diisocyanate and polyol are reacted in the same container with a molar ratio of tolylene isocyanate to isophorone diisocyanate in the range of 50/50 to 97/3, and isocyanate group-terminated prepolymer. The process of preparing the main agent containing
The equivalent ratio of diethyltoluenediamine, 4,4'-methylenebis (N-sec-butylaniline) and plasticizer to diethyltoluenediamine and 4,4'-methylenebis (N-sec-butylaniline) is 40/60 to 97. A method comprising the step of mixing to prepare a curing agent in the range of 3/3. The method according to claim 4, wherein the step of preparing the main agent comprises a step of reacting isophorone diisocyanate with a polyol in a container, and then a step of adding tolylene diisocyanate into the container and further reacting.