KR100663186B1 - Silane modified polyurethane waterproofing membrane composition and manufacturing method thereof - Google Patents

Abstract

Provided is a silane-modified polyurethane waterproofing coating composition, which shows excellent durability, chemical resistance, adhesion, anti-aging property, ozone resistance, weather resistance and heat resistance while using no catalyst or curing agent, and has excellent workability. The silane-modified polyurethane waterproofing coating composition comprises: a silane-modified polyurethane obtained by reacting an isocyanate-endcapped prepolymer having an NCO index of 2-2.5, theoretical NCO(%) of 10-15 and a weight average molecular weight of 100,000 or more, aminemethoxysilane and epoxyethoxy silane; a polyoxyethylene succinic anhydride-based dispersant; a polyacrylate methoxypropyl acetate-based dispersant; a polyoxyethylene propylene block copolymer-based defoaming agent; calcium carbonate; talc; anti-oxidant; zinc oxide; anti-aging agent; and magnesia.

Description

Silane modified polyurethane waterproofing membrane composition and manufacturing method thereof

The present invention relates to a silane-modified polyurethane coating waterproofing composition and a method for manufacturing the same, and more particularly, durability, chemical resistance, adhesion, aging resistance, ozone resistance, weather resistance and heat resistance, and curing time is fast and bubbles are not generated. The present invention relates to a silane-modified one-component polyurethane coating waterproofing composition having excellent workability during construction and a method of manufacturing the same.

Polyurethane materials for civil engineering and construction are capable of seamless construction, which is a characteristic of the material itself, and chemical properties such as construction properties that adhere well to complex types of structures, adhesion to the surface, chemical resistance and durability, and sound absorption. Its physical properties, such as dimensional stability and excellent elongation, in particular, due to its great advantage in following the cracking of the lower leg, the demand for building interior, exterior wall and floor waterproofing of the building is increasing. However, at present, polyurethane materials having such excellent characteristics for construction are produced by isocyanate prepolymer and polyol mixture in the production plant, and they must be constructed through several steps of weighing, blending, stirring, and construction according to the mixing ratio determined at the construction site. Since defects in the tops are likely to occur and skilled professionals are required, it is a cause of increase in labor costs, which in turn increases the construction cost and reduces the construction efficiency.

In general, two-component polyurethane materials have to use both agitated waterproofing materials within a limited pot life, so the time interval between agitation and construction must be well controlled, and if the time is not correct, the amount of material loss increases. Therefore, in order to maintain the excellent physical and chemical properties of these polyurethane materials and to compensate for the shortcomings of the two-component type, one-component formulations of polyurethane building materials have been studied. For example, an NCO wt% content of 1-5% isocyanate prepolymer is studied. It synthesize | combines, and adds a filler, stabilizer, a coloring agent, etc., and uses the method of one-component polyurethane material. However, this method has a disadvantage in that the curing time is slow at room temperature and only a little moisture is present, and storage stability is deteriorated, and swelling defects of the coating film are easily generated by carbon dioxide generated by the reaction of water and isocyanate. To compensate for this disadvantage, Japanese Patent Publication No. 5-75035 discloses a method of improving storage stability and curing rate by using a catalyst of morpholino diethyl ether. However, this method did not solve the occurrence of defects caused by swelling of the coating film caused by carbon dioxide. Therefore, in order to solve this problem, US Patent No. 4720535 or Japanese Patent Laid-Open Publication No. 4-226522 discloses a method using a seed base which is a latent curing agent. In other words, aldehyde is reacted with primary di or triamine to form polyadimine, and then mixed with an isocyanate prepolymer and used as a one-component material.

However, when the poly-aldimine is mixed with an isocyanate and used as a one-component urethane material, the reactivity is fast in a high temperature and high humidity environment, and thus there is an inadequate problem in waterproofing the roof of a building in summer. That is, the hardening of the surface and the bottom of the coating proceeds easily, but the inside of the coating is difficult to penetrate moisture from the hardened coating surface, so that the progress of curing is slow and swelling defects are frequently caused by aldehydes dissociated during curing.

As another method of using latent curing agents, British Patent No. 1575666 discloses a method of monolithizing a secondary amine with a ketone or an aldehyde to form a polyenamine and mixing it with an isocyanate prepolymer. In this case, however, the isocyanate of the prepolymer must be masked or an isocyanate having a very low reactivity should be used, and it is difficult to use as a building material because of low storage stability. In addition, Korean Patent Publication No. 1997-0065579 states that aldimine and ketamine are present at the same time to adjust the curing rate so that the defect rate is low and construction is possible under adverse environmental conditions such as high temperature and humidity, but the same problem as other patents mentioned above. It implies

The technical problem to be achieved by the present invention is to solve the problems described above without using a catalyst or latent curing agent, durability, chemical resistance, adhesion, aging resistance, ozone resistance, weather resistance and heat resistance and excellent curing time and bubbles Does not occur is to provide a silane-modified polyurethane coating waterproof material composition excellent in workability during construction.

Another object of the present invention is to provide a method for producing the silane-modified polyurethane coating waterproofing composition.

In order to achieve the above technical problem, in the present invention, NCO INDEX is obtained by reacting an isocyanate terminated prepolymer, an amine methoxysilane and an epoxy ethoxysilane having a weight average molecular weight of 100,000 or more prepared in a range of 2 to 2.5 and a theoretical NCO% of 10 to 15. Silane modified polyurethanes; Polyoxyethylene succinic anhydride-based dispersants; Polyacrylate methoxypropyl acetate type dispersant; Polyoxyethylene propylene block copolymer antifoaming agent; Calcium carbonate; Talc; Antioxidants; Zincation; Anti-aging agents; And provides a silane-modified polyurethane coating film waterproofing composition comprising magnesia.

Another technical problem of the present invention is an isocyanate terminated prepolymer, an aminemethoxysilane and an epoxyethoxysilane having a NCO INDEX of 2 to 2.5 and a theoretical NCO% of 10 to 15, having a weight average molecular weight of 100,000 or more at 90 to 100 ° C. Reacting to obtain a silane-modified polyurethane; And

Polyoxyethylene succinic anhydride type dispersant, polyacrylate methoxypropyl acetate acetate type dispersant, polyoxyethylene propylene block copolymer type antifoaming agent, calcium carbonate, talc, antioxidant, zincation By the method of producing a silane-modified polyurethane coating waterproofing composition comprising the step of adding and mixing the antioxidant and magnesia at 30 to 50 ℃.

Hereinafter, the present invention will be described in more detail.

The coating film waterproofing material of the present invention is a silane-modified polyurethane containing a polyurethane modified with aminemethoxysilane and epoxyethoxysilane as a main component, and has excellent durability, chemical resistance, adhesion, aging resistance, ozone resistance, weather resistance, and heat resistance. In addition, the hardening time is fast and bubbles are not generated, so it has excellent workability during construction, and the problem that occurs in the existing one-component polyurethane waterproofing agent, namely, the hardening of the surface and the bottom of the coating proceeds easily, but the inside of the coating is cured. It is a coating waterproofing material of new construction civil engineering structure that is difficult to penetrate moisture from the surface of coating film, so that the progress of curing is slow and swelling defects caused by aldehydes dissociated during curing are not frequently generated.

The method for producing the silane-modified one-part polyurethane coating film waterproofing composition of the present invention as described above is as follows.

First, amine methoxysilane and epoxy ethoxysilane were added to an isocyanate terminated prepolymer having an NCO INDEX of 2 to 2.5 and a theoretical NCO% of 10 to 15 to a weight average molecular weight of 100,000 or more, and reacted at 90 to 100 ° C. to modify the silane. Prepare polyurethane. Herein, a solvent is added during the reaction, and specific examples of the solvent include toluene, xylene, DMF, and the like. And the content of the solvent is 30 to 50 parts by weight based on 100 parts by weight of the isocyanate terminated prepolymer. If the content of the solvent exceeds the above range, the solid content decreases, so that the mechanical strength is lowered. If the content of the solvent is below the range, the viscosity is high, and thus it is not preferable because it is difficult to prepare a coating waterproof agent.

In particular, the reaction temperature is preferably about 95 ° C. If the reaction temperature is less than 90 ° C, the reactivity of the isocyanate terminal prepolymer, the aminemethoxysilane and the epoxy ethoxysilane is lowered, and the reaction temperature is higher than 100 ° C. It is not preferred because addition reactants are formed.

The reaction time varies depending on the reaction temperature but is preferably in the range of 1 to 10 hours, especially 2 to 3 hours.

It is preferable that the content of the amine methoxysilane is 10 to 20 parts by weight in 100 parts by weight of the isocyanate terminated prepolymer, and the content of the epoxy ethoxysilane is 10 to 20 parts by weight in 100 parts by weight of the isocyanate terminated prepolymer. If the content of amine methoxysilane and epoxy ethoxysilane is less than 10 parts by weight, respectively, residual isocyanate groups may be present in the prepolymer, which may cause swelling by reacting with moisture during construction.In addition, if the content exceeds 20 parts by weight, the viscosity of the prepolymer is high. It is difficult to manufacture a film waterproofing agent.

The mixing ratio of the epoxy ethoxysilane is preferably 100 to 130 parts by weight based on 100 parts by weight of the aminemethoxysilane.

If the content of the epoxy ethoxysilane exceeds 130 parts by weight based on 100 parts by weight of the amine methoxysilane, unreacted silane is present, and if it is less than 100 parts by weight, the adhesive strength decreases, which is not preferable.

The isocyanate terminated prepolymer is a substance that reacts with aminemethoxysilane and epoxyethoxysilane to form a urethane bond. For example, hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI) and aliphatic isocyanate compounds, And / or aromatic isocyanate compounds such as toluene diisocyanate (TDI). Among them, it is preferable to use an aliphatic isocyanate compound such as H ₁₂ MDI from the viewpoint of weatherability.

The isocyanate terminated prepolymer is preferably prepared in the range of 2 to 2.5 NCO INDEX and the theoretical NCO mole% in the range of 10 to 15. If the NCO INDEX and the theoretical NCO mole% are out of the above range, it is preferable in terms of hardness and mechanical strength of the coating film. I can't. The weight average molecular weight of the isocyanate terminated prepolymer is preferably 100,000 or more, in particular 120,000 to 150,000.

When carried out according to the above procedure, a silane-modified polyurethane having a solid content of 50 to 65% by weight, in particular 60% by weight is obtained. The remainder except for the solid content is a solvent component such as toluene and xylene described above.

Polyoxyethylene succinic anhydride dispersant, polyacrylate methoxypropyl acetate acetate dispersant, polyoxyethylene propylene block copolymer antifoaming agent, calcium carbonate, talc, antioxidant, zincation The anti-aging agent and magnesia are mixed and stirred at 30 to 50 ° C., particularly at 40 ° C., to prepare a silane-modified one-component polyurethane coating waterproofing composition. Wherein said mixing and stirring time is 2 to 3 hours.

The polyoxyethylene succinic anhydride type dispersant and the polyacrylate methoxy propylene acetate type dispersant are dispersants capable of producing a high-solid coating film waterproofing agent without using an additional solvent in the silane-modified polyurethane. The nick anhydride-based dispersant uses a viscosity of 200 cps or less, particularly 150 to 180 cps, specific gravity 1.01 to 1.05, particularly about 1.03, acid value 110 to 113, especially about 112.

If the viscosity, specific gravity and acid value of the polyoxyethylene succinic anhydride-based dispersant are out of the above range, it is not preferable in terms of uniform dispersibility.

In addition, the polyacrylate methoxypropyl acetate-based dispersant is a specific gravity of 1.05 to 108, about 1.07, water 0.5 or less, in particular 0.1 to 0.3, viscosity of 300 cps or less in particular 250 to 280 cps is used.

If the specific gravity, moisture, and viscosity of the polyacrylate methoxypropyl acetate dispersant are out of the above range, it is not preferable in terms of controlling the particle size of the dispersion.

The content of the polyoxyethylene succinic anhydride-based dispersant and the polyacrylate methoxypropyl acetate acetate-based dispersant is preferably 5 to 10 parts by weight based on 100 parts by weight of the silane-modified polyurethane. If the content of the dispersant is less than 5 parts by weight, the dispersion is not good, the viscosity of the product is high, and if it exceeds 10 parts by weight, the water resistance of the coating film is lowered, it is not desirable to decrease the physical properties when immersed in water for a long time.

The content of the polyacrylate methoxypropyl acetate-based dispersant is preferably 100 to 150 parts by weight based on 100 parts by weight of the polyoxyethylene succinic anhydride-based dispersant. As a substance having a function of removing bubbles, a polyoxyethylene propylene block copolymer antifoaming agent having a pH of 7.5 and water of 1.0% is used. The content of the antifoaming agent is preferably 5 to 10 parts by weight based on 100 parts by weight of the silane-modified polyurethane. If the content of the antifoaming agent is less than 5 parts by weight, a large amount of bubbles are generated during dispersion, and if it exceeds 10 parts by weight, it is not preferable to generate oil spots on the surface of the coating film.

The content of calcium carbonate used in the present invention is preferably 20-50 parts by weight based on 100 parts by weight of the silane-modified polyurethane. If the content of calcium carbonate is less than 20 parts by weight, it is difficult to secure the thickness of the coating film when the coating material is applied because the total solid content is less. If the content is more than 50 parts by weight, the viscosity is high and the physical properties are not preferable.

The content of the talc is preferably 10-20 parts by weight based on 100 parts by weight of the silane-modified polyurethane for the same reason as calcium carbonate.

The antioxidant functions to prevent yellowing, and specific examples thereof include cerium neodecanoate and rare earth octate, and the content thereof is preferably 9-10 parts by weight based on 100 parts by weight of the silane-modified polyurethane. Do. If the content of the antioxidant is less than 9 parts by weight, yellowing occurs and the original color of the coating is decolorized, and if it exceeds 10 parts by weight, aggregates are formed, which is not preferable.

The zincation is also known as zinc oxide functions as a high temperature stabilizer, the content thereof is preferably 4-6 parts by weight based on 100 parts by weight of the silane-modified polyurethane. If the zinc content is less than 4 parts by weight, it is not preferable because the resistance to radiation heat and ultraviolet rays generated after the coating waterproofing agent is applied on the roof of the building is not strong, and more than 6 parts by weight affects the storage stability of the product.

Specific examples of the anti-aging agent include phenyl alpha naphthylamine and triazine antioxidant, and the content thereof is preferably 9-10 parts by weight based on 100 parts by weight of the silane-modified polyurethane. If the content of the anti-aging agent is less than 9 parts by weight, the thermal and static anti-aging effect is weak, and if it exceeds 10 parts by weight, it is undesirable because other additives and shock phenomenon occurs.

The amount of magnesia is preferably 4-6 parts by weight based on 100 parts by weight of the silane-modified polyurethane. If the content of magnesia is less than 4 parts by weight, the presence of moisture on the concrete surface, the adhesive strength is lowered, and if it exceeds 6 parts by weight, the adhesion with the same material is undesirably undesirable.

The silane-modified polyurethane waterproofing composition obtained according to the above process is an isocyanate terminated prepolymer, an aminemethoxysilane and an epoxyethoxysilane having a NCO INDEX of 2 to 2.5 and a theoretical weight average molecular weight of 100,000 or more prepared in the range of 10 to 15. Silane-modified polyurethane obtained by reaction, polyoxyethylene succinic anhydride type dispersant, polyacrylate methoxypropyl acetate acetate type dispersant, polyoxyethylene propylene block copolymer type antifoaming agent, calcium carbonate, talc, antioxidant, zincation, aging It consists of an inhibitor and magnesia.

When the silane-modified polyurethane waterproofing composition having the above-described composition is applied to building civil engineering structures using spray, rubber spatula, trowel, etc., it exhibits excellent tensile strength, low temperature flexibility, impact resistance, adhesiveness, chemical resistance and abrasion resistance once. Even if it is applied to a thickness of 2mm, the curing time is fast, the surface cracking and bubbles of the coating film does not occur, and the durability is excellent, it can effectively prevent the aging phenomenon of the structure due to leakage.

Hereinafter, the present invention will be described with reference to the following examples, but the present invention is not limited to the following examples.

Example  One

15 parts by weight of aminemethoxysilane, 100 parts by weight of dicyclohexylmethane diisocyanate terminal prepolymer having an NCO INDEX of 2 to 2.5 and a theoretical NCO% of 10 to 15 in a weight average molecular weight of about 120000 The addition was carried out for 2 hours to 3 hours at 95 ° C to prepare a silane-modified polyurethane having a solid content of about 60% by weight.

7 weight part of polyoxyethylene succinic anhydride type dispersing agent, 7 weight part of polyacrylate methoxypropyl acetate type dispersing agent, and polyoxyethylene propylene block copolymer type antifoamer to 100 weight part of said 60 weight% silane modified polyurethanes 6 parts by weight, 30 parts by weight of calcium carbonate, 15 parts by weight of talc, 9.5 parts by weight of cerium neodecanoate from Uniroyal, an antioxidant, 5 parts by weight of zinc, 9 parts by weight of triazine antioxidant from Uniroyal, an antioxidant, and 5 parts by weight of magnesia was mixed and stirred at 40 ° C. for 2 to 3 hours to prepare a silane-modified one-component polyurethane coating waterproofing composition.

Example  2

The silane-modified one-part polyurethane coating film waterproofing material composition was carried out in the same manner as in Example 1, except that 80 parts by weight of the silane-modified polyurethane having 60% by weight of solid content was used instead of 100 parts by weight of the silane-modified polyurethane having 60% by weight of solid content. Was prepared.

Example  3

The silane-modified one-component polyurethane coating waterproofing material composition was carried out in the same manner as in Example 1, except that 80 parts by weight of the silane-modified polyurethane having 60% by weight of solid content was used instead of 100 parts by weight of the silane-modified polyurethane having 60% by weight of solid content. Was prepared.

Evaluation example

Bubble generation amount, curing time, and tension by comparing the coating film waterproofing composition prepared according to Examples 1 to 3 and the polyurethane waterproofing material product (commercially manufactured according to Korean Patent Publication No. 1997-0065579) as a reference example Strength, elongation, adhesion strength, breathability, water absorption and chemical resistance were evaluated and the results are shown in Table 1 below.

TABLE 1

division Example Reference Example One 2 3 Tensile Strength (N / mm ² ) 25 23 19 13 Elongation (%) 700 650 630 600 Adhesive strength (N / mm ² ) 2.5 2.3 2.0 1.5 Permeability (g / m ^2/24 hours) 7.8 7.3 7.0 5.8 Absorption rate (%) 0.3 0.3 0.3 0.5 Chemical resistance Ethylene glycol clear clear clear clear Calcium chloride clear clear clear Bad Gasoline clear clear clear Bad Motor oil clear clear clear clear Sodium chloride clear clear clear Bad Bubble generation amount (number / 1m ² ) 0 One One 5 Curing time (1 mm, hr) 3 4 4 10

From the results of Table 1, the silane-modified one-component polyurethane waterproofing material of the present invention has excellent tensile strength and elongation rate as compared to the case of the reference waterproofing material composition, does not generate bubbles during construction, and has a fast curing time even at a thickness of 2mm coating. It can be seen that it is very excellent in both the workability and the workability.

As described above, the silane-modified one-component polyurethane coating waterproofing composition according to the present invention has excellent durability, chemical resistance, adhesiveness, aging resistance, ozone resistance, weather resistance and heat resistance, fast curing time, and no bubbles are generated. It has excellent workability during construction, and the problem that occurs in the existing one-component polyurethane waterproofing agent, that is, the surface and the bottom of the coating harden easily, but the moisture inside the coating film is hard to penetrate from the hardened coating surface. It is possible to prevent the occurrence of swelling defects caused by aldehydes that are slow and dissociate during curing.

The above-described silane-modified one-component polyurethane coating waterproofing composition is able to maintain a strong resistance to cracks in concrete structures, and because it forms a highly durable waterproof layer that does not generate bubbles, it is very useful as a coating waterproofing material for roofs and civil structures of building structures. It can be usefully used.

Claims (5)

Silane-modified polyurethanes obtained by reacting isocyanate terminated prepolymers, aminemethoxysilanes and epoxyethoxysilanes having a weight average molecular weight of 100,000 or more with an NCO INDEX of 2 to 2.5 and a theoretical NCO% of 10 to 15; Polyoxyethylene succinic anhydride-based dispersants; Polyacrylate methoxypropyl acetate type dispersant; Polyoxyethylene propylene block copolymer antifoaming agent; Calcium carbonate; Talc; Antioxidants; Zincation; Anti-aging agents; And silane-modified polyurethane coating waterproofing composition comprising magnesia. According to claim 1, wherein the content of the amine ethoxysilane is 10 to 20 parts by weight based on 100 parts by weight of the isocyanate terminal prepolymer, the content of the epoxy ethoxysilane is 10 to 20 based on 100 parts by weight of the isocyanate terminal prepolymer Silane-modified polyurethane coating film waterproofing composition, characterized in that it is part by weight. According to claim 1, wherein the content of the polyoxyethylene succinic anhydride-based dispersant is 5 to 10 parts by weight based on 100 parts by weight of the silane-modified polyurethane, The content of the polyacrylate methoxypropyl acetate-based dispersant is 5 to 10 parts by weight based on 100 parts by weight of the silane-modified polyurethane, The content of the polyoxyethylene propylene block copolymer antifoaming agent is 5 to 10 parts by weight based on 100 parts by weight of the silane-modified polyurethane, The content of the calcium carbonate is 20 to 50 parts by weight based on 100 parts by weight of the silane-modified polyurethane, The talc content is 10 to 20 parts by weight based on 100 parts by weight of the silane-modified polyurethane, The antioxidant content is 9 to 10 parts by weight based on 100 parts by weight of the silane-modified polyurethane, The zinc content is 4 to 6 parts by weight based on 100 parts by weight of the silane-modified polyurethane, The amount of the antioxidant is 9 to 10 parts by weight based on 100 parts by weight of the silane-modified polyurethane, The content of the magnesia is 4 to 6 parts by weight based on 100 parts by weight of the silane-modified polyurethane, characterized in that the silane-modified polyurethane coating waterproofing composition. According to claim 1, wherein the polyoxyethylene succinic anhydride-based dispersing agent has a viscosity of 200 cps or less, specific gravity 1.01 to 1.05, acid value of 110 to 113, The polyacrylate methoxypropyl acetate-based dispersant is a silane-modified polyurethane coating film waterproofing composition, characterized in that the specific gravity of 1.05 to 108, water 0.5 or less, viscosity 300cps or less. An isocyanate terminated prepolymer, an aminemethoxysilane, and an epoxyethoxysilane having a NCO INDEX of 2 to 2.5 and a theoretical NCO% of 10 to 15 in a weight average molecular weight of 100,000 or more were reacted at 90 to 100 ° C. Obtaining; And Polyoxyethylene succinic anhydride type dispersant, polyacrylate methoxypropyl acetate acetate type dispersant, polyoxyethylene propylene block copolymer type antifoaming agent, calcium carbonate, talc, antioxidant, zincation Method for producing a silane-modified polyurethane coating waterproofing composition comprising the step of adding and mixing the anti-aging agent and magnesia at 30 to 50 ℃.