JPH0586817B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention provides a cold-curing water-based polymer in which a crosslinking agent captured by a first polymer and a second polymer crosslinked by the crosslinking agent are dispersed in water in the form of fine particles. The present invention relates to compositions and methods of using the same. [Prior art] Conventionally, aqueous emulsion type compositions used as adhesives and paints are cured by crosslinking the main chain of the polymer by reacting with a crosslinking agent during the film formation process in order to increase film strength. It is being done. There are two types of such aqueous emulsion type compositions: those using a crosslinking agent that reacts at room temperature and those using a crosslinking agent that reacts at high temperatures. [Problems to be Solved by the Invention] In an aqueous emulsion type composition using a crosslinking agent that reacts at room temperature, if the polymer and the crosslinking agent are blended in advance, the crosslinking reaction will proceed during storage etc. and the aqueous emulsion type composition will It thickens and hardens, making it impossible to coat. Therefore, the polymer and crosslinking agent are kept separated in separate containers until used, and are mixed together each time they are used. However, it is cumbersome to mix the two liquids each time they are used. Moreover, if the compound is not used up within a certain period of time, the remaining amount will thicken and harden over time, which is inconvenient and uneconomical. In addition, in aqueous emulsion type compositions that use a latent crosslinking agent that reacts only at high temperatures, the crosslinking reaction does not occur at room temperature, and the polymer and crosslinking agent can be blended in advance, so the above-mentioned disadvantages do not occur. Since a heating device is required to cause the crosslinking reaction, it has the disadvantage that the heating device and the like are costly. The present invention was made in view of the above circumstances, and it is an object of the present invention to provide an aqueous room-temperature curable composition that uses a crosslinking agent that reacts at room temperature and that does not require separate holding of the polymer and the crosslinking agent, and a method for using the same. purpose. [Means for solving the problems] In order to achieve the above object, the present invention has the following features.
The first gist is a cold-curable aqueous composition in which component (A) and component (B) are dispersed in water in the form of fine particles, and (A) a first polymer that captures a polyfunctional compound. (B) A second polymer having a functional group that reacts with a functional group of a polyfunctional compound in its molecular structure. A polymer that captures a polyfunctional compound (first polymer) and a second polymer that has a functional group that reacts with the functional group of the polyfunctional compound in its molecular structure are each dispersed in water in the form of fine particles at room temperature. A curable aqueous composition is prepared, and the room-temperature curable aqueous composition is applied to the surface to be treated and water is evaporated to react with the polyfunctional compound-trapping polymer and the functional groups of the polyfunctional compound in the molecular structure. The second gist is a method of using an aqueous room-temperature curable composition that forms a polymer coating film by contacting it with a polymer having a functional group. The present inventors have found that in an aqueous emulsion-type composition using a room-temperature-reactive crosslinking agent, the polymer and the crosslinking agent are separated and brought into contact after the composition is applied. We thought that the crosslinking reaction would not occur during storage even if the material was stored, and in order to realize this, we conducted a series of studies using various materials. As a result, by using a polyfunctional compound as a crosslinking agent, capturing it in the first polymer, and dispersing it in the form of fine particles in water, an emulsion is created in which the polyfunctional compound crosslinking agent is blocked from water, and A polymer having a group that reacts with the functional group of the polyfunctional compound crosslinking agent (second
It has been found that the desired purpose can be achieved by creating an emulsion of the polymer (polymer) and mixing the two to form an aqueous emulsion type composition. That is, in this composition, the polyfunctional compound crosslinking agent is in a trapped state, and the solubility of the polyfunctional compound in water is low, and the surfactant used has a low emulsifying ability for the polyfunctional compound. Since the diffusion of the polyfunctional compound through the phase is extremely restricted, crosslinking reactions do not occur during storage, etc., and after application of the emulsion type composition, the polyfunctional compound crosslinking agent bleeds out only when water evaporates, causing the above-mentioned The second polymer is crosslinked and a tough coating film is formed. Next, this invention will be explained in detail. A schematic diagram of the room temperature curable aqueous composition of the present invention is shown in FIG.
As shown in the figure. The room temperature curable aqueous composition of the present invention includes water 1, a polyfunctional compound 2 which is a crosslinking agent, a first polymer 3 that captures the water, and a functional group in the molecular structure that reacts with the functional group of the polyfunctional compound. The first polymer 3 and the second polymer 4 contain surfactants 5 and 6, respectively.
emulsified and dispersed in water 1. As is clear from Figure 1, polyfunctional compound 2
is captured by the first polymer 3, and this capture polymer 3 has surfactant 5 oriented in a micelle shape around its outer periphery and dispersed in the water 1 in the form of fine particles. In this way, the polyfunctional compound 2 which is a crosslinking agent
is entrapped in the first polymer 3. On the other hand, the second polymer 4, which has a functional group that reacts with the functional group of the polyfunctional compound in its molecular structure, is dispersed in water in the form of particles by the surfactant 5.
It is still in a stable condition. The polyfunctional compound 2 that acts as the crosslinking agent includes an epoxy group, an amino group, a carboxyl group,
Examples include those having two or more functional groups such as a hydroxyl group, an amide group, and an N-methylolamide group in the molecule. Examples of the polyfunctional epoxy compound include:
Diglycidyl ether of bisphenol A, diglycidyl ether of brominated bisphenol A,
Examples include polycarboxylic acid polyglycidyl ether, alkane polyol polyglycidyl ether, and epoxy novolak. Examples of polyfunctional amine compounds include aromatic polyamines such as metaphenylene diamine, linear aliphatic polyamines such as diethylene triamine, triethylene triamine, and hexamethylene diamine, cyclic aliphatic polyamines commercially available as curing agents for epoxy resins, and fatty acids. Examples include polyamine adducts, ketoimines, modified aliphatic polyamines, and polyamide amines. Examples of polyfunctional carboxyl compounds include aliphatic polycarboxylic acids with relatively large aliphatic chains such as hexamethylene dicarboxylic acid, aliphatic polycarboxylic anhydrides, terephthalic acid, isophthalic acid, pyromellitic acid, and pyromellitic acid dicarboxylic acid. Examples include anhydride, benzophenonetetracarboxylic acid, benzophenonetetracarboxylic dianhydride, and the like. The polyfunctional compound 2 may be liquid or solid at room temperature or the reaction temperature during the preparation of the first polymer 3, as long as it is ultimately captured by the first polymer 3. I don't mind. however,
If a material that is liquid at room temperature is used, the bleed rate when the first and second polymers 3 and 4 come into contact is fast, probably because the molecules move easily, and the coating film strength develops quickly. The first polymer 3 that captures the polyfunctional compound 2 includes styrene, styrene derivatives, butadiene,
These include monomers or copolymers of monomers having ethylenically unsaturated bonds such as acrylonitrile, chloroprene, acrylic esters, methacrylic esters, vinyl acetate, ethylene, vinyl chloride, and vinylidene chloride. In addition, the second polymer 4, which has a functional group that reacts with the functional group of the polyfunctional compound in its molecular structure, reacts with the functional group of the polyfunctional compound so that, for example, the functional groups are distributed at appropriate intervals in the molecular chain. When a monomer that has a functional group that reacts with the functional group and an ethylenically unsaturated bond is copolymerized with a monomer that does not have a functional group that reacts with the functional group of a polyfunctional compound and has an ethylenically unsaturated bond, It is obtained by Monomers having a functional group that reacts with the functional group of the polyfunctional compound and having an ethylenically unsaturated bond include a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an N-methylolamide group,
Examples include monomers having sulfonic acid groups, etc. in the molecule. Here, the monomer having a hydroxyl group is, for example, allyl alcohol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, monoallyl ether of polyhydric alcohol. etc., and monomers with carboxyl groups include, for example, acrylic acid, methacrylic acid, itaconic acid, fumaric acid,
These include unsaturated polymerizable organic acids such as crotonic acid, maleic acid monoester, itaconic acid monoester, fumaric acid monoester, and maleic acid. Furthermore, monomers having an amino group include, for example, allylamine,
tert-butylaminoethyl methacrylate, etc., monomers having an epoxy group include glycidyl acrylate, glycidyl methacrylate, etc., and monomers having an N-methylolamide group include N-methylol acrylamide, N-methylol Examples of monomers having a sulfonic acid group include vinylsulfonic acid and styrenesulfonic acid. In addition, monomers that have an ethylenically unsaturated bond and do not have a functional group that reacts with the functional group of a polyfunctional compound include, for example, styrene, styrene derivatives, butadiene, acrylonitrile, methacrylonitrile, and acrylic esters. , methacrylic acid ester, vinyl acetate, ethylene, vinyl chloride, vinylidene chloride, etc. The second polymer 4 obtained by copolymerizing these monomers has a functional group in the molecule that reacts with the functional group of the polyfunctional compound, so when it comes into contact with the polyfunctional compound 2, it crosslinks and hardens. It has the following characteristics. As the surfactants 5 and 6 used in the present invention, any of anionic surfactants, cationic surfactants, and nonionic surfactants may be used, such as polyoxyethylene lauryl ether, polyoxyethylene nonyl ether, and polyoxyethylene nonyl ether. enyl ether, polyoxyethylene sorbitan monostearate, etc. Additionally, water-soluble polymers such as starch, dextrin, methyl cellulose, carboxymethyl cellulose, polyacrylic acid or its water-soluble salt, polyacrylamide or its water-soluble copolymer, polyvinyl alcohol, water-soluble polyamide, etc. may be used. . The above surfactants can be used alone or in combination of two or more. The surfactant 5 for emulsifying and dispersing the first polymer and the surfactant 6 for emulsifying and dispersing the second polymer may be of the same kind or different. The room temperature curable aqueous composition of the present invention is produced using the above-mentioned raw materials, and the production is carried out, for example, as follows. First, an emulsion of a polyfunctional compound-trapping polymer is made. A method for producing this is, for example, a method in which a monomer, which is a raw material for the first polymer, is subjected to emulsion polymerization in water in the coexistence of a polyfunctional compound to trap the polyfunctional compound in the first polymer particles (hereinafter referred to as "coexistence method"). ), and a method in which a polyfunctional compound is added to an aqueous emulsion of a first polymer prepared by a known method while stirring, and the polyfunctional compound is absorbed into the first polymer particles (hereinafter referred to as a "post-absorption method"). ) can be mentioned. In both the coexistence method and post-absorption method,
If the polyfunctional compound diffuses into the aqueous phase, a crosslinking reaction will occur if it coexists with the second polymer. To prevent this, the polyfunctional compound is efficiently captured in the first polymer. There must be. For this purpose, it is necessary to satisfy the following conditions. (1) The solubility of polyfunctional compounds in water is low. (2) The surfactant used has a low emulsifying ability for polyfunctional compounds. (3) The first polymer has an affinity for the polyfunctional compound to the extent that it can capture the polyfunctional compound. Furthermore, in addition to the above conditions, during polymerization of the first polymer, it is desirable that very little surfactant be present separated from the polymer particles after polymerization. In the case of the above coexistence method, the solubility of the polyfunctional compound in water, the emulsifying ability of the surfactant used for the polyfunctional compound itself, and the
By appropriately selecting the weight ratio of the polyfunctional compound to the polymer, the affinity of the polyfunctional compound to the first polymer to be produced, the Tg (glass transition temperature) of the polymerized polymer, etc., the ratio of (aqueous phase)/(first The distribution ratio of the polyfunctional compound (polymer phase of
partitioned into the polymer phase of 0% concentration in water.
It is possible to produce an emulsion that looks like this. In this method, if the polyfunctional compound is one that easily reacts under acid or alkali conditions, such as an epoxy compound, it is desirable to maintain the pH of the system near neutrality during polymerization. On the other hand, the post-absorption method is a method in which the polyfunctional compound is later absorbed into the particles of the first polymer already present in the emulsion by diffusing it into water. In order to make the particles absorb polyfunctional compounds,
Compared to the above-mentioned coexistence method, trace amounts of polyfunctional compounds tend to remain in the water. However, while the coexistence method described above may result in insufficient polymerization stability of the first polymer, this post-absorption method does not cause this problem.
Moreover, it has the advantage of being easy to operate. In addition, when absorbing a polyfunctional compound in the post-absorption method, it is preferable to heat the emulsion to a temperature higher than the Tg of the first polymer because the absorption rate becomes faster. Thus, the emulsion of the multifunctional compound-trapping polymer is determined by the ease of absorption of the multifunctional compound into the first polymer (depending on the viscosity, whether it is liquid or solid, etc.), the polymerization stability of the first polymer, etc. can be obtained by appropriately selecting one of the methods in consideration of the required pot life and the like. However, solvents with high solubility for polyfunctional compounds, such as toluene, acetone, ethanol,
This does not mean that methanol and the like cannot be mixed with water and used; it is possible to use methanol as long as the concentration of the polyfunctional compound in the water is low after the polyfunctional compound-trapping emulsion is produced. Note that the proportion of the polyfunctional compound can be selected within the range of 2 to 1000% with respect to the first polymer. However, if there are too few polyfunctional compounds,
Not much crosslinking effect can be obtained after film formation. In addition, in order to trap a large amount of the polyfunctional compound in the first polymer, rather than obtaining the first polymer by polymerizing only with monomers with low polarity such as styrene, ethylene, isoprene, and butadiene,
It is preferable to copolymerize polar monomers such as acrylic esters, methacrylic esters, and vinyl acetate, and monomers with higher polarity such as acrylonitrile, methacrylonitrile, vinyl chloride, and vinylidene chloride. The content of these monomers is preferably about 10 to 100% in the case of slightly polar monomers, and about 1 to 50% in the case of more polar monomers, based on the total monomers. In addition, during the production of the polyfunctional compound-trapping polymer, it is also possible to copolymerize a monomer having a functional group that reacts with the functional group of the polyfunctional compound, such as a hydroxyl group, a carboxyl group, or an amino group. . In this case, the trapping polymer is crosslinked with a portion of the polyfunctional compound, so that the mobility of the polymer segment can be controlled by changing the degree of crosslinking, and as a result, the rate of desorption of the polyfunctional compound can be controlled. However, if the amount of copolymerization of a monomer having a functional group that reacts with the functional group of the polyfunctional compound is too large, the polyfunctional compound will promote crosslinking of the polyfunctional compound-trapping polymer itself, causing movement of the polymer segments. becomes excessively suppressed, thereby
Even if the captured polyfunctional compound tries to act as a crosslinking agent for the final target polymer, it becomes difficult to release the multifunctional compound from the captured polymer, and it does not function smoothly. Therefore, it is desirable that the copolymerized amount of the monomer having a functional group that reacts with the functional group of the polyfunctional compound is kept at 10% or less of the total monomers. Also, double bonds such as divinylbenzene can be
Monomers having one or more monomers can also be used to control the elimination of polyfunctional compounds, but for the same reason as above, the amount should be kept to 10% or less of the total monomers. In addition, during the above-mentioned copolymerization, a known polymer modifier or the like may be allowed to coexist, if necessary. In the thus obtained aqueous emulsion of a polyfunctional compound-trapping polymer, the polyfunctional compound serving as a crosslinking agent is dispersed in water in the form of particles.
Since it is trapped in the polymer and does not exist in water, the crosslinking reaction will not proceed even if it is mixed in the same liquid with the second polymer that undergoes the crosslinking reaction. After producing the multifunctional compound-trapping polymer emulsion as described above, an aqueous emulsion of a second polymer is then produced using known emulsion polymerization techniques. That is, in water in the presence of a surfactant that has a dispersion stabilizing effect, a monomer that has a functional group that reacts with the functional group of a polyfunctional compound and has an ethylenically unsaturated bond, and the functional group of the polyfunctional compound. By copolymerizing a monomer that does not have a functional group that reacts with the polyfunctional compound and has an ethylenically unsaturated bond, a second polymer that has a functional group that reacts with the functional group of the polyfunctional compound is produced. As a result, an aqueous emulsion of polymer 2 is obtained. In addition,
The copolymerization amount of monomers with functional groups is
It is desirable to set it to about 0.1 to 30%. In the aqueous emulsion of the second polymer obtained in this way, the second polymer having a functional group that reacts with the functional group of the polyfunctional compound is dispersed in water as particles by the use of a surfactant as a dispersion stabilizer. It is in the same condition as it is. Next, the aqueous emulsions of the first and second polymers are mixed such that the molar ratio of the functional group of the polyfunctional compound to the functional group that reacts with this functional group is 0.8 to 1.2. As a result, the room temperature curable aqueous composition of the present invention is obtained. The room-temperature curable aqueous composition obtained in this way has a polyfunctional compound as a crosslinking agent and a crosslinked polymer mixed in the same solvent.
The crosslinking agent is captured by the first polymer and does not diffuse into water, thus preventing the crosslinking reaction from proceeding. This is the greatest feature of this invention. This aqueous composition is extremely stable for six months or more at room temperature without thickening or gelling. Then, when the composition is applied to the surface to be treated and water is volatilized, the polyfunctional compound-trapping polymer (first polymer) and the crosslinked polymer (second polymer) are formed.
come into contact with. The polyfunctional compound then bleeds and reacts with the functional groups in the second polymer to form a cured film. The above-mentioned crosslinking reaction progresses over time, and depends on the types of functional groups of the polyfunctional compound and the second polymer, the affinity between the polyfunctional compound and the first polymer, and the first polymer of the polyfunctional compound.
This can be controlled by changing the distribution within the polymer particles. Although the trapping polymer that traps the polyfunctional compound is not supposed to essentially contribute to crosslinking, it actually forms a network-like structure in which the molecular chains of the resulting polymer and its own molecular chains are entangled. Maybe because it becomes
Even if a coated film that has been formed and left for about a month is immersed in an organic solvent, almost no elution occurs. As described above, in the room temperature curable aqueous composition of the present invention, the crosslinking reaction does not occur even though the crosslinking agent and the crosslinked polymer are mixed in the same solvent. It is a one-component product that is maintained without thickening or curing, and only when it is applied at the time of use does a crosslinking reaction proceed, forming a film and curing, making it extremely easy to use. [Effects of the Invention] As described above, the room-temperature curable aqueous composition of the present invention does not undergo crosslinking reaction between the crosslinking agent and the crosslinked polymer as long as water does not volatilize, that is, in the emulsion state, and the initial state remains unchanged. In order to maintain the temperature, there is no need to separate and hold the crosslinking agent and the crosslinked polymer in separate containers as in conventional room temperature curable aqueous compositions. Furthermore, since it is not a two-component type, there is no need to mix the two together each time it is used, and it is sufficient to apply only the required amount to the surface to be coated. Therefore, it is extremely easy to use. That is, when the composition of the present invention forms a film and the water evaporates, it becomes insoluble in the solvent after one day, and the crosslinking density increases over time. Moreover, since no high-temperature-reactive crosslinking agent is used, no heating is required during curing, resulting in good workability. The room temperature curable aqueous composition of the present invention can be used in a wide range of applications such as adhesives and paints. For example, as an adhesive, it is initially sticky and has excellent initial adhesive strength to bond adherends, and as time passes, the crosslinking density improves and the adhesive strength in the equilibrium state increases, making it an excellent adhesive. is obtained. In addition, in paints, the initial crosslinking density is low, so film forming properties are good, and over time the paint film crosslinks, increasing the hardness of the paint film and improving stain resistance. You can get something. Next, examples will be described. [Example 1] First, an aqueous emulsion of a polyfunctional compound-trapping polymer was obtained by a coexistence method. That is, 91.6 g of water and 2 g of Emulgen 935 (manufactured by Kao Soap Co., Ltd.), a surfactant, were placed in a 300 ml four-necked flask equipped with a thermometer, stirrer, condenser, and dropping funnel.
2 g of Emulgen 920 (manufactured by Kao Soap Co., Ltd.), 0.1 g of sodium bisulfite, and 0.2 g of trisodium phosphate were added and dissolved. Next, after purging the inside of the flask with nitrogen gas and keeping the system at 70°C, 44 g of methyl methacrylate, 3 g of acrylonitrile, 28 g of 2-ethylhexyl acrylate, and 25 g of epoxy resin (Epicote #828, manufactured by Yuka Ciel Co., Ltd.) were added. A mixture of dissolved monomers and 10 g of water in which 0.3 g of ammonium persulfate (polymerization initiator) was dissolved were added dropwise over 3 hours using separate dropping funnels.
Thereafter, it was kept for 2 hours to complete the reaction. the result,
In the acrylic polymer (first polymer) particles,
Polymerization rate 100%, in which the epoxy compound is captured
A stable aqueous emulsion with a solids content of approximately 50% was obtained. Next, an aqueous emulsion of a second polymer having a functional group that reacts with the functional group of the polyfunctional compound was obtained. That is, in a 300 ml capacity four-necked flask equipped with a thermometer, stirrer, condenser, and dropping funnel, 91.6 g of water, 2 g of Emulgen 935 (manufactured by Kao Soap Co., Ltd.) as a surfactant, and 2 g of Emulgen 920 (manufactured by Kao Soap Co., Ltd.) were added. )
2 g and 0.1 g of sodium bisulfite were added and dissolved. Next, replace the inside of the flask with nitrogen gas,
While keeping the system at 70°C, a mixture of 52 g of methyl methacrylate, 44 g of 2-ethylhexyl acrylate, 8 g of tert-butylaminoethyl methacrylate, and 10 g of water in which 0.3 g of ammonium persulfate was dissolved was added for 3 hours while stirring. The mixture was added dropwise using separate dropping funnels over a period of time, and then kept for 2 hours to complete the reaction. Then, an aqueous emulsion of a second polymer having an amino group that reacts with an epoxy group, which is a functional group of a polyfunctional compound, was obtained. The thus obtained aqueous emulsion of the first polymer (hereinafter abbreviated as "EM1") and the second polymer
Aqueous emulsion of polymer (hereinafter referred to as “EM2”)
) were mixed in a ratio of 32.9/100 to obtain a room temperature curable aqueous composition of the present invention. [Example 2] EM1 and EM2 were obtained in the same manner as in Example 1, but
In the production of EM2, the monomers to be copolymerized are
By using 6.25 g of an 80% aqueous acrylic acid solution in place of 8 g of tert-butylaminoethyl methacrylate, a stable emulsion having a carboxyl group in the polymer and a polymerization rate of 100% was obtained. and
EM1 and EM2 were mixed at a ratio of 52.7/100 to obtain a room temperature curable aqueous composition of the present invention. [Example 3] EM1 and EM2 were obtained in the same manner as in Example 1, but
In the production of EM1, 12.5 g of Epicure U (manufactured by Yuka Ciel Co., Ltd.), an aliphatic amine-based epoxy resin curing agent, was used instead of the epoxy resin Epicote #828, and the amine compound was captured in the polymer. An emulsion with a solid content of 100% and a solid content of 47% was obtained. In addition, in the production of EM2, tert-
Using 8 g of glycidyl methacrylate instead of 8 g of butylaminoethyl methacrylate, a stable emulsion with an epoxy group in the polymer and a polymerization rate of 100% was obtained. And EM1 and EM2
were mixed at a ratio of 22.3/100 to obtain a room temperature curable aqueous composition of the present invention. [Examples 4 and 5] EM1 was obtained by the post-absorption method. That is, in the same reaction apparatus as in Example 1, 91.6 g of water, 2 g of Emulgen 935 (manufactured by Kao Soap Co., Ltd.) as a surfactant,
Dissolve 2 g of Emulgen 920 (manufactured by Kao Soap Co., Ltd.) and 0.1 g of sodium bisulfite. After purging the inside of the flask with nitrogen gas and keeping the system at 70°C, a monomer mixture in which 44 g of methyl methacrylate, 3 g of acrylonitrile, and 28 g of 2-ethylhexyl acrylate were dissolved and 0.3 g of potassium persulfate (polymerized 10 g of water in which an initiator was dissolved was added dropwise over a period of 3 hours using a separate dropping funnel. After that, it was kept for 2 hours to complete the reaction, and the polymerization rate was 100.
%, a stable emulsion with a solids content of 43% was obtained. To 100 g of this emulsion, 14 g of trimethylolpropane polyglycidyl ether (Epicote GE-100, manufactured by Yuka Ciel Co., Ltd.) was added and kept at 40°C for 6 hours with stirring to trap the epoxy compound in the acrylic polymer particles. An emulsion with a solids content of about 50% was obtained. This emulsion EM1 and EM2 used in Example 1 or EM2 used in Example 2 were mixed in the proportions shown in Table 1 to obtain a room temperature curable aqueous composition of the present invention. The compositions of the room temperature curable aqueous compositions of Examples 1 to 5 above are summarized in Table 1.

【table】

〔test〕

Regarding the above five types of room temperature curable aqueous compositions,
After 1 day of mixing, the mixture was poured onto a polyethylene plate to a film thickness of 0.5 mm, and a film was formed in a constant temperature bath at 20°C, and about 0.1 g of the coating film was taken 1 day, 1 month, and 6 months after the film was formed. It was immersed in 40 g of toluene, and the swelling rate and elution rate of coating film-forming components after 24 hours were measured. Similar measurements were also performed on a film formed one month after mixing. The results are shown in Table 2.

【table】

[Table] From the results in Table 2, all of the room temperature curable aqueous compositions showed solvent resistance to the extent that the coating film did not dissolve after one day of film formation, and the swelling rate and elution rate decreased over time. It can be seen that the crosslink density increases over time. Moreover, when comparing the swelling rate and elution rate of the membranes formed one day after mixing and one month after mixing, there is almost no difference, so it is possible to mix the polyfunctional compound as a crosslinking agent and the crosslinked polymer in the same aqueous system. It can be seen that almost no crosslinking reaction occurred even after one month. In addition, epoxy-amine combinations with high reactivity at room temperature (Example 1,
In cases 3 and 4), the crosslinking was almost completed in one month, but in the case of epoxy-carboxyl combinations with low reactivity (Examples 2 and 5), the crosslinking progressed by 1 month.
It's still progressing months later. In addition, EM1 used in Example 1 was heated at 20000 rpm, 1
Pour 10 ml of the liquid phase centrifuged for 1 hour into a flask with a stopper, add 1N-HCl-CaCl ₂ reagent (47.5 ml of HCl,
Add 2 c.c. of CaCl ₂ (405 g, water 300 g) and shake at 30°C for 1 hour, then add 5 c.c. of 0.5N-KOH reagent.
The epoxy concentration in the aqueous phase determined by back titration with 0.5N-HCl solution showed a value of 0.01% or less. The reason why both emulsions are stable even when mixed is that the polyfunctional compound is present in a small amount in the aqueous phase and its solubility is low, and the polyfunctional compound is not emulsified by the surfactant in water. It can be considered that this is because the multifunctional compound as a crosslinking agent is restricted from diffusing into the aqueous phase and reacting with the second polymer for two reasons.

[Brief explanation of drawings]

The drawing is a schematic diagram of the room temperature curable aqueous composition of the present invention. DESCRIPTION OF SYMBOLS 1... Water, 2... Polyfunctional compound, 3... First polymer, 4... Second polymer, 5, 6... Surfactant.

Claims (1)

[Scope of Claims] 1. A room temperature curable aqueous composition characterized in that the following components (A) and (B) are dispersed in water in the form of fine particles. (A) First polymer capturing a polyfunctional compound. (B) A second polymer having a functional group that reacts with a functional group of a polyfunctional compound in its molecular structure. 2. A polymer that captures a polyfunctional compound (first polymer) and a second polymer that has a functional group that reacts with the functional group of the polyfunctional compound in its molecular structure,
A room-temperature-curing aqueous composition, each of which is dispersed in fine particles in water, is prepared, and the room-temperature-curing aqueous composition is applied to the surface to be treated to evaporate water, thereby combining the polyfunctional compound-trapping polymer and the above-mentioned polyfunctional compound-trapping polymer. A method for using an aqueous room-temperature curable composition, which comprises forming a polymer coating film by contacting a polymer having a functional group that reacts with a functional group of a polyfunctional compound in its molecular structure.