KR100594822B1 - Manufacturing Method Of One Pack Urethane System - Google Patents

Abstract

A method for producing a one-component polyurethane system having excellent storage stability is disclosed. First, a mixture comprising a filler, a plasticizer, a colorant, an antifoaming agent and a dispersant and a solvent having a boiling point in the range of 50 to 130 ° C. and incompatible with water are mixed in the range of 10 to 100% by weight based on the amount of the mixture. The resulting mixture is heated to reflux the solvent and at the same time water is separated. After the separated water is removed, the solvent is removed by vacuum evaporation and an inert gas is added, and the one-component polyurethane resin is added in a range of 20 to 200% by weight based on the amount of the mixture and mixed. And a solvent is added to the resin mixture obtained in order to adjust a viscosity and solid content, and the one-component polyurethane system obtained here is packaged. Even if manufactured with a one-component polyurethane system, it is excellent in storage stability and can be applied to the field as it is.

Description

Manufacturing Method Of One-Pack Polyurethane System

The present invention relates to a manufacturing method of a one-component polyurethane waterproofing / flooring system, more specifically, one-packing (one-packing) can be used immediately in the field without any mixing and blending, especially waterproof materials for civil engineering and buildings The manufacturing method of the 1-component polyurethane system which can be used for building materials, such as a flooring material, a sealant, an adhesive agent, etc.

Polyurethane material was introduced in the early 80's for civil and construction use, which enables seamless construction, which is a characteristic of the material itself, and has a construction characteristic that is well adapted to complex structures. In addition, it has excellent chemical properties such as adhesion to chemicals, chemical resistance and durability, and physical properties such as sound absorption and dimensional stability. In particular, polyurethane material has excellent trackability against cracking under the ground because of its great elongation. The demand is increasing as waterproofing materials for inner, outer walls and floors of buildings.

However, currently, polyurethane systems having such excellent properties for construction are generally used as two-component systems based on isocyanate prepolymers and curing agents composed of additives such as polyol mixtures, fillers, pigments, dispersants, and antifoaming agents. . In other words, the subject and the curing agent must be applied through various steps such as metering, blending, stirring, and construction according to the compounding ratio set at the construction site, thus causing construction defects and requiring skilled workers. . It is pointed out that the problem of reducing construction efficiency by raising construction cost as a whole. In addition, since the two-component polyurethane system usually requires the use of a mixture of all the systems within a limited working time, it is necessary to control the time interval between agitation and construction well, and there is a problem that a large amount of material loss occurs when this time is not correct.

Therefore, in recent years, research has been actively conducted on the one-component formation of polyurethane building materials to compensate for the disadvantages of two-component type while maintaining the excellent physical and chemical properties of the polyurethane material.

For example, a method of synthesizing an isocyanate prepolymer having an NCO wt% content of about 1 to 5% and adding a filler, a stabilizer, a colorant, and the like to one-component polyurethane material is used. However, this method has a disadvantage in that the curing time is slow at room temperature, and even if only a few moisture is present in the material, the storage stability is lowered 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 Laid-Open No. 5-75035 discloses a method for improving storage stability and curing rate by using a morpholino die ether ether catalyst. However, this method causes the occurrence of defects that cause swelling of the coating film by carbon dioxide.

Therefore, in order to solve this problem, US Patent No. 4,720,535 and Japanese Patent Laid-Open No. 4-226522 propose a method of using a latent curing agent (Shiff's base). In other words, aldehyde is reacted with primary di or triamine to make poly aldimine, which is mixed with isocyanate prepolymer and used as a one-component material. However, when the poly aldimine is mixed with an isocyanate to be used as a one-component urethane material, there is an inadequate problem in waterproofing the roof of a building in summer due to high reactivity in a high temperature and high humidity environment. That is, the hardening of the surface and the bottom of the coating proceeds easily, but the penetration of moisture from the hardened coating surface is difficult, and thus the curing progress is slow and swelling defects are caused by aldehydes dissociated during curing.

In another method using latent curing agents, British Patent No. 1575666 discloses a method of forming a polyeneamine by reacting a ketone or an aldehyde with a secondary amine, and mixing it with an isocyanate prepolymer to form a one-part. In this case, however, the isocyanate of the prepolymer should be masked or an isocyanate having a very low reactivity should be used, and the storage stability is low, making it difficult to use as a building material. In order to overcome these disadvantages, Korean Patent No. 0192201 discloses Shiff ′s base, a latent curing agent in which aldehydes and ketimines exist in one chain by reacting aldehydes and ketones with diamines, and the moisture-curable one-component poly A method for preparing a urethane composition has been disclosed.

In summary, most of the disclosed inventions disclose only synthesis and introduction of various types of latent curing agents to solve problems on storage stability and curing mechanisms. That is, their disclosed inventions only refer to the polyurethane resin portion, not to the method of making the overall system. However, the polyurethane system used as a building material is composed of a mixed form in which a polyurethane resin causing hardening and other additives such as fillers, pigments, dispersants, antifoaming agents and the like for imparting physical properties and properties are introduced. In other words, the one-component polyurethane system is a comprehensive system that includes a resin part and other additives, and is moisture-curable even when a very good latent curing agent is used. Therefore, if a small amount of water is present in any one of the components, the essential storage stability is essential. Difficult to secure

In other words, the storage stability is poor due to moisture present in the filler (e.g. calcium carbonate), which is a component of the additive used in the one-component system, and the storage period (storage stability) is short. have.

In order to improve this, the filler is dried using various types of drying furnaces, but in this case, the equipment and drying cost are additionally reduced, resulting in low price competitiveness. According to the dry drying method, the drying time is long, and the complete moisture Difficult to remove In addition, when drying in such a drying furnace there is a problem that the storage method is difficult because it must be stored and used after mass drying.

 Accordingly, an object of the present invention is to add a isocyanate prepolymer, a filler, and other additives to various types of latent curing agents to secure a storage stability, and to manufacture a fully one-component polyurethane building material system that minimizes manufacturing and facility investment costs. Existing two-component system is a one-piece solution that completely solves the problems of reducing construction efficiency and requiring the use of a mixed system within a limited working time. It provides a method of manufacturing a polyurethane system for building materials.

In order to achieve the above object of the present invention in the present invention

A mixture comprising at least one of a filler, a plasticizer, a colorant, an antifoaming agent and a dispersant and a solvent having a boiling point in the range of 50 to 130 ° C. and incompatible with water are mixed in the range of 10 to 100% by weight based on the amount of the mixture. step;

Heating the resulting mixture to reflux the solvent and simultaneously separating water;

Removing the solvent after removing the separated water;

Adding and mixing the one-component polyurethane resin in the range of 20 to 200% by weight as solids based on the amount of the mixture while introducing an inert gas;

Adding a solvent to adjust the viscosity and solids of the resulting resin mixture; And

It provides a method for producing a one-component polyurethane system comprising the step of packaging the resulting one-component polyurethane system.

According to the present invention, a one-component polyurethane system having excellent storage stability can be easily manufactured, and a polyol mixture (a mixture of polyols, fillers, pigments, and various additives) based on isocyanate prepolymers and used as a curing agent is uniform at the site of use. The problem of the existing system used for the use of waterproofing or flooring by mixing in the mixing ratio is solved.

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

As the filler used in the present invention, it is preferable to use calcium carbonate, talc, silica, barium sulfate, kaolin, clay and the like in the range of 30 to 50 parts by weight. In addition, a flow preventing filler may be used for wall or sealing purposes. For example, it is preferable to use aliphatic amide waxes, fume-silica, and surface-treated bentonite within the range of 1 to 20 parts by weight.

Plasticizers include general plasticizers such as dioxyl phthalate, dibutyl phthalate, dioxyl adipate, diisodecyl phthalate and diisononyl phthalate, and flame retardant plasticizers such as triphenyl phosphate, tricresyl phosphate and trisisopropylphenyl phosphate. It is used alone or in combination according to the 5 to 20 parts by weight.

As the colorant, colorants such as mixed pigments colored by carbon black, titanium dioxide, chromium oxide green, chromium green or organic pigments can be used within the range of 2 to 10 parts by weight.

As the other additive, an antifoaming agent and a dispersant may be used, and these may be used in the range of 0.05 to 2.0 parts by weight, respectively.

In addition, as the applicable solvent, at least one selected from the group consisting of toluene, benzene and xylene may be preferably used. They have a breaking point between 50 ° C. and 130 ° C. without mixing with water, and their amount is preferably in the range of 10 to 100% by weight based on the weight% of the mixture. And it is preferable to remove water by refluxing for 30 minutes to 3 hours in the temperature range of 50 ℃ to 130 ℃. The heating temperature may be maintained at a level suitable for reflux of the solvent, but is usually performed in a temperature range of 100 ± 10 ℃.

The amount of water removed varies depending on the storage conditions of the fillers, plasticizers, colorants, and various additives and the raw materials used, and their removed shapes can be seen by checking the water separated from the receiver tank. When the separation of the water is finished, remove the water from the receiver tank. Thereafter, the inside of the reactor is evacuated and the solvent is completely removed. The solvent can be recovered and used again as a reflux solvent in the next reaction.

Through this process, it is possible to remove the moisture content in the mixture of the filler, plasticizer, colorant, and various additives to 300 ppm or less. Then, the one-component polyurethane resin is added.

As the one-component polyurethane resin, as the moisture-curable polyurethane prepolymer resin, an isocyanate prepolymer alone or an isocyanate prepolymer may be used in which a moisture-curable latent curing agent is included. It is preferable to use the usage-amount of these 1-component polyurethane resin in 20-200 weight% of solid content of 1-component polyurethane resin with respect to the weight% of the said mixture obtained. If the added amount of the one-component polyurethane resin is less than 20% by weight, the content of the resin is less than the required physical properties, and when used more than 200% by weight, the increase in physical properties according to the added amount is insignificant. When, it doesn't mean much. Therefore, the amount thereof is to be in the above-described range, and more preferably in the range of 30 to 70% by weight.

Wherein the isocyanate prepolymer as a one-component polyurethane resin is an aliphatic or aromatic diisocyanate, a modified isocyanate, or a polymeric isocyanate in diols or triols of polyetherpolyols, polyesterpolyols, hydroxylpolycarbonates, or the like or mixtures thereof. A chain extender or the like is reacted to synthesize a prepolymer having an isocyanate content of 2 to 10% by weight relative to the weight of the prepolymer.

The aromatic diisocyanate used at this time is 2,4 / 2,6-toluene diisocyanate (TDI 80/20), 2,4-toluene diisocyanate (TDI 100), 4,4'-diphenylmethane diisocyanate (Monomeric MDI) etc. are preferable, and as aliphatic diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate, hydrogenated diphenylmethane diisocyanate, and 1, 6- hexamethylene diisocyanate are preferable. As the modified isocyanate, trade names COSMONATE LL, COSMONATE LK, and COSMONATE LT produced by Kumho Mitsui Toatsu Co., Ltd. may be preferably used. As the polymeric isocyanate, M-100, produced by Kumho Mitsui Toatsu Co., Ltd. M-200, M-300, M-400 and the like can be preferably used.

As the polyether polyol, diols or triols having a molecular weight of 400 to 6000 are preferable, and molecular weights of 1000 to PP-1000, PP-2000, PP-3000, GP-3000, GP-4000, etc., produced by Korea Polyol Co., Ltd. Polyether polyols up to 4000 may be more preferably used.

The polyester polyol preferably has an average molecular weight of 500 to 6000 by reacting polycarboxylic acid and polyhydric alcohol by condensation reaction, especially SE-1714, SE-1541, SE-2014 produced by Samsung Polymer. More preferably, polyester polyols having a molecular weight of 1000 to 3000 may be used.

Other polycarbonates having two or more active hydrogens in one molecule, polytetramethylene ether polyols, polycaprolactone polyols, polybutadiene polyols, polyether polyols, or polymer polyols obtained by grafting vinyl monomers to polyester polyols alone Or it can mix and use.

Chain extenders to increase the hardness and physical properties of urethanes include ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, tripropylene glycol, trimetholpropane, glycerin Etc. can be used. These chain extenders are more reactive than polyols and increase the viscosity of the final isocyanate prepolymers, so they are limited to use in the range of 1 to 10 weight percent of the polyols.

In addition, the moisture-curable latent curing agent is a morpholine such as morpholino dimethyl ether, poly aldehyde made by reacting aldehyde with primary di or triamine using Shiff's base, ketone or aldehyde to secondary amine The reaction of ketones and aldehydes to polyenamines, divalent or trivalent primary amines made by the reaction of the polyamines, polydiamine-ketamine with the presence of aldimine and ketamine in the same chain, a mixture thereof may be used.

One-component polyurethane resin is added and mixed under a nitrogen atmosphere for 30 minutes to one hour, and a solvent is added to adjust the viscosity and solids content of the one-component polyurethane system. Examples of solvents that can be used include methyl ethyl ketone, Ketones such as acetone, aromatic hydrocarbons such as toluene and xylene, petroleum solvents such as mineral spirit, or cellulose acetate, butyllulsolve, etc. may be used, which is 1 to 20% by weight based on the amount of the resin mixture obtained. Can be used within the range. If the added amount is less than 1% by weight, the viscosity is high and workability is bad and affects the smoothness of the surface. If the amount is more than 20% by weight, it is caused by the volatilization of the solvent on the curing mechanism. Therefore, it is preferable to set it as said range, and it is most preferable to use in 5 to 10 weight% range.

Thereafter, the nitrogen atmosphere is removed and vacuum degassing is performed to remove bubbles in the one-component polyurethane system, thereby preparing a one-component polyurethane system.

Next, as a packaging step, the one-component polyurethane system prepared in this way is placed in a container, and a method of sealing after injecting dry nitrogen, and then removing the air by vacuum, and the like may be preferably applied. More preferably, it is a method of storing the inlet of the container facing downward after packaging.

Hereinafter, preferred embodiments of the present invention will be described in detail.

<Example 1>

Rotating the impeller in a 1,500 L reactor, 90 Kg of toluene, 68 Kg of DOP (Dioctylphthalate), 315 Kg of bicarbonate (NC-6000 of Woojin Chemical Co., Ltd.), 1.5 Kg of antifoaming agent (BYK-066 of BYK) and colorant (DOP: Chrome Green = 1 45 kg of the mixture was milled at a ratio of 1). And the temperature was heated up to 100 degreeC. At this time, reflux occurred and toluene was refluxed to the receiver tank. After refluxing for about 1 hour, the receiver tank was observed to confirm that water was separated.

Water was separated from the receiver tank, and vacuum was applied to remove all solvents in the reactor, and nitrogen was added to adjust the pressure to atmospheric pressure. While continuously adding nitrogen, the temperature was lowered to 60 ° C. using cooling water, and 440 Kg of one-component polyurethane binder resin (Hebschem Co., Ltd. VAROCOAT-ONE SP-60VA) was added to adjust the viscosity and solid content. 51 kg was added and mixed for at least 30 minutes. And in order to remove the physical bubbles present in the reactants by performing a vacuum degassing for 30 minutes using a vacuum pump to prepare a one-component polyurethane system according to the present invention.

<Example 2>

The same procedure as in Example 1 was carried out, except that the one-component polyurethane resin was changed to Hepchem Chem VAROCOAT-ONE SP-70VA instead of Hepchem Chem VAROCOAT-ONE SP-60VA. Urethane systems were prepared.

Comparative Example 1

Rotating the impeller in a 1,500 L reactor, 90 kg of toluene, 68 kg of DOP (Dioctylphthalate), bicarbonate (NC-6000 of Woojin Chemical Co., Ltd.), 315 Kg, 1.5 Kg of antifoaming agent (BYK BYK-066) and colorant ( 45 Kg of a mixture milled at a ratio of DOP: chrome green = 1: 1 was added thereto. And after raising the temperature to 100 ℃ mixed for 30 minutes while flowing dry nitrogen. Then, after the temperature was lowered to 60 ° C., 440 Kg of one-component polyurethane binder resin (Hebschem Co., Ltd. VAROCOAT-ONE SP-60VA) was added thereto and mixed for 30 minutes or more. In order to remove the physical bubbles present in the reactants by using a vacuum pump vacuum degassing for 30 minutes to prepare a one-component polyurethane system.

Comparative Example 2

A one-component polyurethane system was prepared in the same manner as in 1, but using an isocyanate prepolymer (NCO% = 1.5%, PPG / TDI Type) instead of the one-component polyurethane binder resin.

Comparative Example 3

The comparison was carried out in the same manner as 1, but was changed to dried for at least 12 hours at 100 ℃ as heavy coal to prepare a one-component polyurethane system.

The storage stability, coating film formation time, and bubble generation phenomena of the one-component polyurethane system prepared according to Examples 1 and 2 and Comparative Examples 1, 2 and 3 above were shown in Table 1 below.

Here, the method of checking the storage stability is to inject contents into a 1 liter square steel can, filled with dry nitrogen gas, covered with a lid, and treated with Teflon tape for sufficient sealing, and then prepared several identical samples and left at room temperature for hours. Confirmed according to. The coating film formation time was applied to each system to a thickness of 1mm and confirmed that the surface hardening and complete curing, and the bubble formation phenomenon of the cross-section of the coating film was cut into the cross section after curing, and the bubble formation state was observed.

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Storage stability Over 1 year Over 1 year 164 hours 89 hours 193 days Surface hardening 2.5 hours 2.2 hours 1.5 hours 6.3 hours 2.5 hours Fully cured 8.3 hours 8.8 hours 5.4 hours 16.4 hours 7.4 hours Paint cross section No bubble No bubble No bubble Bubbles No bubble

As shown in Table 1, in the case of the one-component polyurethane system manufactured using the method of the present invention, the storage stability was remarkably excellent, the curing time was appropriate, and there was no internal bubble of the cross section. Unlike the comparative example, this method can be seen that it is an excellent manufacturing process that is economically competitive in a method that can be manufactured without a separate drying furnace.

According to the present invention as described above, since the effect of economically reducing the amount of water present in the filler, plasticizer, colorant and various additives is economically significant, the storage stability is excellent even when the existing two-component polyurethane system is manufactured as a one-component polyurethane system. Because it can be stored for a long time, it is possible to apply it on site as it is.                     

Although the above has been described with reference to the preferred embodiments of the present invention, those skilled in the art can variously modify and change the present invention without departing from the spirit and scope of the present invention as set forth in the claims below. It will be appreciated.

Claims (8)

Mixtures comprising at least one of fillers, plasticizers, colorants, antifoams and dispersants, and solvents having a boiling point in the range of 50-130 ° C. and incompatible with water, in the range of 10-100% by weight, based on the amount of the mixture Making; Heating the resulting mixture to reflux the solvent and simultaneously separating water; Removing the solvent after removing the separated water; Adding and mixing the one-component polyurethane resin in the range of 20 to 200% by weight as solids based on the amount of the mixture while introducing an inert gas; Adding a solvent to adjust the viscosity and the amount of solids of the resulting resin mixture; And A method for producing a one-component polyurethane system comprising the step of packaging the resulting one-component polyurethane system. The method of claim 1, wherein the filler is at least one selected from the group consisting of calcium carbonate, talc, silica, barium sulfate, kaolin, clay, aliphatic amide wax, fume-silica and surface-treated bentonite. Way. The group according to claim 1, wherein the plasticizer is composed of dioxylphthalate, dibutyl phthalate, dioxyl adipate, diisodecyl phthalate, diisononyl phthalate, triphenyl phosphate, tricresyl phosphate, and trisisopropylphenyl phosphate. At least one selected from the manufacturing method. The method according to claim 1, wherein the colorant is at least one selected from the group consisting of carbon black, titanium dioxide, chromium oxide green, chromium green, and mixed pigments colored by mixing organic pigments. The method of claim 1, wherein the heating is performed at a temperature range of 100 ± 10 ° C., and the reflux time is in the range of 30 minutes to 3 hours. The method according to claim 1, wherein the solvent is at least one selected from the group consisting of toluene, benzene and xylene. The method according to claim 1, wherein the water content in the mixture obtained after separating the water is 300 ppm or less. The solvent of claim 1, wherein the solvent added to adjust the viscosity and the amount of solids of the resin mixture is at least selected from the group consisting of methyl ethyl ketone, acetone, toluene, xylene, mineral spirits, cellulsolve acetate and butyl celusolve; One, and the amount thereof added is in the range of 1 to 20% by weight based on the total amount of the system.