KR20150133689A - Sorbent coating fluid, sorbent-supporting metal plate obtained by applying sorbent coating fluid, and heat exchanger having sorbent-supporting metal plate - Google Patents

Abstract

In the metal plate supporting the sorbent using the organic polymer-based sorbent, since the sorbent has the property of swelling by including water, the sorbent coating film is formed on the metal plate by using a solvent containing a large amount of water There is a problem that cracks are generated in the sorbent coating film formed by shrinkage of the sorbent at the time of drying. Furthermore, the adhesion to the metal plate is also poor, and there is a problem that the sorption agent coating film is peeled off under conditions such as watering. DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-described conventional circumstances, and an object of the present invention is to provide a coating agent for a sorbent agent which does not cause cracking or peeling, and a metal plate coated with the coating solution.
An organic polymeric sorbent particle comprising a carboxyl group and an organic polymer having a crosslinking structure, a cationic polymer adhered to the surface of the sorbent, a binder resin, an alcohol and water.

Description

TECHNICAL FIELD [0001] The present invention relates to a sorption agent coating metal, a sorption agent coating metal, a sorption agent coating metal, a sorbent coating metal, a sorbent coating metal, a sorbent coating metal, -SUPPORTING METAL PLATE}

The present invention relates to a sorption agent coating liquid, a sorption agent-carrying metal plate formed by coating the sorption agent coating solution, and a heat exchanger having the sorption agent-supporting metal plate.

Conventionally, adsorption type heat exchangers such as adsorption type refrigerators and adsorption type air conditioners are known as the applications of the metal plate carrying the adsorbent. This type of adsorption heat exchanger is disclosed in, for example, Patent Documents 1 and 2 and 3.

As an adsorbent supported on a metal substrate of the adsorption heat exchanger, an inorganic adsorbent such as silica gel or zeolite is used in Patent Document 1, and a polymer adsorbent is used in Patent Documents 2 and 3.

The organic polymer-based sorbents disclosed in Patent Documents 2 and 3 have properties of swelling and shrinking by moisture absorption and desorption. This flexible structure does not cause deterioration of hygroscopic performance due to structural breakage caused by repetition of moisture absorptive and desorptive wetting shown in inorganic materials. In addition, a larger amount of water can be absorbed than an inorganic adsorbent.

However, since the organic polymer-based sorptive agent has a property of swelling by including water, when a coating solution is combined with a solvent containing a large amount of water to prepare a sorptive coating film, the organic polymer- There is a problem that cracks are generated in the sorbent coating film formed by the volume change from the swelling of the agent to the contraction state. In addition, the adhesion to the base material is also poor, and there is a problem that the sorption agent coating film is peeled off under conditions such as water immersion. With respect to the former problem, Patent Document 3 discloses a method in which an organic solvent-based sorbent is carried on a heat exchanger in a contracted state by using an alcohol solvent as a main solvent. However, the moisture content in the slurry must be strictly controlled. In this example, the problem of adhesion to the substrate to be supported is not discussed.

Japanese Unexamined Patent Publication No. 5-322364 Japanese Patent Laid-Open No. 2006-200850 Japanese Patent Application Laid-Open No. 2010-270972

As described above, in the case of the metal plate supporting the sorbent using the organic polymer-based sorbent, there was a problem such as cracking and peeling of the sorbent layer. DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-described conventional circumstances, and an object of the present invention is to provide a coating agent for a sorbent agent which does not cause cracking or peeling, and a metal plate coated with the coating solution.

As a result of intensive studies, the inventors of the present invention have found that the above object can be achieved by the presence of a cationic polymer having a charge opposite to that of an organic polymer-based sorptive agent in a solvent system containing a large amount of water, and has reached the present invention .

That is, the present invention is achieved by the following means.

(1) An organic polymer-based sorbent particle comprising a carboxyl group and an organic polymer having a crosslinked structure, a cationic polymer adhered to the surface of the sorptive agent, a binder resin, an alcohol and water.

(2) The sorptive coating composition according to (1), which contains 100 to 500 parts by weight of water based on 100 parts by weight of the organic polymeric sorptive.

(3) The coating agent for a sorptive agent according to (1) or (2), wherein the cationic polymer is a cationic urethane resin.

(4) The coating agent for a sorptive agent according to any one of (1) to (3), wherein the binder resin is a neutral urethane resin or a weakly anionic urethane resin.

(5) The sorbent coating liquid according to any one of (1) to (4), which contains polyvinyl alcohol.

(6) A sorption agent-bearing metal sheet having a sorption agent layer formed by coating the sorption agent coating solution according to any one of (1) to (5) on a metal sheet, and further comprising a layer of anionic primer between the sorption agent layer and the metal sheet Characterized in that the sorbent-bearing metal plate is a metal plate.

(7) A heat exchanger having a sorption material-carrying metal plate according to (6).

By using the present invention, even in a solvent system containing a large amount of water, it is possible to reduce the amount of the binder used for suppressing cracking of the formed sorbent layer, and as a result, the amount of the organic polymer- It is possible to suppress the deterioration of the amount and the moisture absorption rate. Therefore, it is effective for a batch-type dehumidification system that absorbs a large amount of moisture for a long time or a secant rotor for repeating moisture absorption and desorption in a short time. In addition, by reducing the hydration of the surface of the organic polymer-based sorbent particles, the adhesion with the binder and the adhesion with the substrate are improved, and a more homogeneous sorbent layer can be formed.

● About sorbent

The organic polymer-based sorbent particles employed in the present invention have a carboxyl group in the molecule and also have a crosslinked structure. The carboxyl groups present in the organic polymeric sorbent particles have the property of chemically adsorbing moisture in the air. The carboxyl group is preferably of a salt type, and the pair cation is not particularly limited, and examples thereof include alkali metals such as Li, Na, K, Rb and Cs, alkaline metals such as Be, Mg, Ca, It is possible to remove organic cations such as earth metals, Cu, Zn, Al, Mn, Ag, Fe, Co and Ni, NH ₄ and amine. Among them, from the viewpoint of moisture absorptive and desorptive rate, it is preferable to be a cation of an alkali metal or alkaline earth metal.

The amount of the carboxyl group is preferably 1 to 10 mmol / g, more preferably 3 to 10 mmol / g. If the amount of the carboxyl group is less than 1 mmol / g, a sufficient moisture absorptive and desorptive property may not be obtained. On the other hand, if the amount exceeds 10 mmol / g, the organic polymer based sorptive agent is absorbed to become a swollen gel state, , The volume change due to the swelling shrinkage becomes so large that the durability of the sorbent layer becomes insufficient. Here, the amount of the carboxyl group indicates the molar amount of the carboxyl group based on the weight of the polymer when all of the carboxyl groups of the polymer are in an acid form when the sorbent having a crosslinked structure includes a carboxyl group in a salt form.

The cross-linking structure of the organic polymer-based sorbent particles reduces the swelling of particles caused by moisture absorption or absorption. Such a crosslinked structure is not particularly limited as long as it is not physically and chemically modified by moisture absorption and moisture absorption, and may be any structure such as crosslinking by covalent bonding, ion crosslinking, intermolecular interaction of polymers or crosslinking by a crystal structure do. Among them, a crosslinked structure by covalent bonding is most preferable from the viewpoint of being strong and stable.

The degree of crosslinking of the organic polymeric-based sorbent agent particles is not limited. However, in order to suppress the swelling when the organic polymer-based sorbent particles absorb or absorb moisture, the crosslinking structure is preferably copolymerized with the crosslinking monomer , It is preferable that the degree of crosslinking calculated by the following formula is 8 or more.

Crosslinking degree = crosslinking monomer (mol) / total monomer (mol) x 100

The particle diameter of the organic polymer-based sorbent particles employed in the present invention is preferably 1 to 60 탆. Among them, it is preferable that the particle diameter is 5 to 50 占 퐉. If the particle diameter is too small, the amount of the binder resin for binding each particle increases, and the coating of the binder resin covers the particles, resulting in a decrease in the moisture absorption rate. On the other hand, when the particle diameter is too large, the dispersibility of the particles in the coating solution to the solvent is lowered, and homogeneous coating becomes difficult, and the moisture absorption performance is deteriorated due to the decrease of the surface area of the organic polymer- Throw away.

As the method for producing the organic polymer-based sorbent particles having the crosslinked structure described above, the following methods can be exemplified.

(1) A method of copolymerizing a monomer having a carboxyl group with a crosslinking monomer

(2) a method of hydrolyzing a copolymer of a monomer capable of inducing a carboxyl group and a crosslinking monomer

(3) a method of crosslinking a polymer having a carboxyl group with a reactive crosslinking agent

(4) a method of crosslinking a polymer having a functional group capable of inducing a carboxyl group with a reactive crosslinking agent and hydrolyzing

Examples of the monomer having a carboxyl group in the method (1) include monomers having a carboxylic acid group such as acrylic acid, methacrylic acid, maleic acid, itaconic acid and vinyl propionic acid, and carboxylic acid salts of these monomers.

In the method of (2), examples of the monomer capable of inducing a carboxyl group include monomers having a nitrile group such as acrylonitrile and methacrylonitrile; And anhydrides, ester derivatives and amide derivatives of monomers having a carboxylic acid group such as acrylic acid, methacrylic acid, maleic acid, itaconic acid and vinyl propionic acid. The functional groups of these monomers are converted into carboxyl groups by hydrolysis.

The crosslinking monomer is not particularly limited as long as it is a monomer having two or more double bonds in the molecule, and examples thereof include glycidyl methacrylate, N-methylol acrylamide, triallyl isocyanurate, triallyl (Meth) acrylate, triethyleneglycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, diethyleneglycol di (meth) acrylate, And crosslinkable vinyl compounds such as methylene bisacrylamide. Among them, the crosslinking structure of triallyl isocyanurate, triallyl cyanurate, divinylbenzene and methylene bisacrylamide can be chemically modified at the time of hydrolysis for introducing a carboxyl group into a crosslinked copolymer containing them It is preferable for use in the case of obtaining a carboxyl group through a hydrolysis step.

The hydrolysis may be carried out by heating the cross-linked copolymer obtained by copolymerization in an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or sodium carbonate or in a basic aqueous solution such as ammonia or the like. Here, since the carboxyl group formed by the hydrolysis forms a salt with the cation corresponding to the agent used for hydrolysis, it is preferable to select a drug to be used for hydrolysis in consideration of a desired salt type. It is also possible to change the salt type of the carboxyl group by performing treatment with an acid or treatment with an aqueous metal salt solution after hydrolysis.

In the method of (4), the polymer having a functional group capable of inducing a carboxyl group is obtained by copolymerizing, for example, a monomer having a functional group capable of reacting with a monomer capable of inducing a carboxyl group as described above and a reactive crosslinking agent . The monomer having a functional group capable of reacting with the reactive crosslinking agent is selected depending on the type of the reactive crosslinking agent to be used. As a specific method, for example, a nitrile-based polymer having a content of vinyl monomer having a nitrile group of 50% by weight or more is reacted with a nitrile group, a hydrazine compound, a polyamine or formaldehyde, Nitrile group and the like in the same manner as in the above (2).

● For cationic polymers

The cationic polymer is a polymer having at least one or more primary or secondary amino groups or quaternary ammonium groups in the molecule and capable of positively charging by polymerizing the polymer chains in an aqueous solution. The positively charged polymer ionically binds to the surface of the organic polymeric sorbent particle, which is an anionic polymer. As a result, the hydration of the surface of the organic polymer-based sorbent particle is reduced and the adhesion with the binder resin component is also improved I think it can be done.

The cationic polymer covers the surface of the organic polymer-based sorbent particles to reduce the hydration of the particles and to improve the adhesion between the binder resin and the particles. It is preferable to have an ammonium group in the functional group. When the cationic polymer is water-soluble or redispersible, it is preferable that the cationic polymer is an aqueous emulsion that does not redisperse in water after drying, because water resistance of the water-absorbent agent layer is a concern. Among them, a cationic urethane resin having excellent adhesion with a binder resin, moisture permeability and the like is preferable.

The amount of the cationic polymer to be added is 1 to 30 parts by weight, particularly preferably 5 to 20 parts by weight, based on 100 parts by weight of the sorptive agent. When the addition amount is decreased, the adhesiveness is lowered. On the other hand, when the addition amount is increased, the proportion of the organic polymer-based sorbent particles is decreased, so that the moisture absorption rate of the formed sorbent layer is lowered.

● About the binder

The cationic polymer alone has a weak bonding force between the particles of the organic polymer-based sorbent agent, and the formed sorbent layer becomes smooth, so that it may be difficult to maintain the sorbent layer under conditions such as water immersion. Therefore, it is preferable that the binder resin has adhesiveness between the organic polymer-based sorbent particle and the cationic polymer and also has adhesion with the primer layer coated on the metal plate. It is also preferable that the binder resin is capable of following the volume change of the organic polymer-based sorbent particles in the formed sorbent agent layer during shrinkage upon drying and swelling upon wetting. From this viewpoint, it is preferable that the binder resin has a glass transition point of 50 캜 or lower desirable. Examples of the resin that can be used as such a binder resin include urethane resins, acrylic resins, and epoxy resins, and neutral or weakly anionic resins are preferable from the viewpoint of difficulty in forming aggregates with the cationic polymer in the coating solution. Among them, an aqueous urethane resin having excellent adhesion, moisture permeability and good dispersibility in a coating liquid is particularly preferable.

The proportion of the binder resin is 20 to 100 parts by weight, particularly preferably 30 to 50 parts by weight, based on 100 parts by weight of the organic polymer-based sorbent agent particles. If the proportion of the binder resin is excessively large, the binder resin portion covering the organic polymer-based sorbent particles may be increased and the moisture absorption rate may be lowered. If too small, the sorbent layer may be cracked or the adhesion may be deteriorated.

It is difficult to form a homogeneous sorbent layer when the application amount of the sorbent coating solution is decreased. However, by adding a polymer having good adhesion and film formability such as polyvinyl alcohol to the binder resin, the film formability of the sorbent coating solution can be improved have. In the case of using polyvinyl alcohol, the addition amount thereof is 1 to 10 parts by weight, preferably 2 to 8 parts by weight, based on 100 parts by weight of the organic polymer-based sorbent agent particles. If the addition amount is too large, the viscosity of the coating solution for the sorbent agent becomes excessively high, which makes it difficult to coat or lower the moisture absorption rate. On the other hand, if the amount is too small, the effect of improving the film formability may not be sufficiently obtained.

● Alcohol and water

The alcohol solvent is added for the main purpose of improving dilution, defoaming and drying rate of the coating liquid for the sorbent agent. There is no particular limitation on the type of alcohol used when the coating liquid for a sorbent agent is combined. However, as higher alcohols are used, the water-dispersible resin tends to dissolve and the viscosity of the coating liquid increases, It is preferable to use a composition containing ethanol as the main component and a low alcohol such as ethanol as the main component. In view of the wettability with the substrate, ethanol is preferably used as the main component.

The content of alcohol in the coating liquid for the sorbent agent is preferably 20 to 500 parts by weight, more preferably 100 to 300 parts by weight, based on 100 parts by weight of the organic polymer-based sorbent agent particles. On the other hand, the water contained in the coating liquid for the sorptive agent is 100 to 500 parts by weight based on 100 parts by weight of the sorptive agent, the sum of the water derived from the cationic polymer and the binder resin component and the water added when the coating liquid for the sorptive agent is adjusted, And preferably 100 to 300 parts by weight. When the amount of water contained in the coating liquid for the sorbent agent is excessively large, there is a problem in that the adhesion of the sorbent layer to the substrate is lowered, the drying rate is lowered, Occurs.

● About coating liquid

The sorbent coating solution of the present invention comprises the above-described organic polymer-based sorbent particles, cationic polymer, binder resin, water, and alcohol as essential components. An antimicrobial agent, an antiseptic, and the like may be added in addition to the essential components as long as they do not impair the moisture absorption performance. As a method of combining the coating agent for a sorptive agent, there is a method of dispersing organic polymeric sorptive agent particles in a dispersion medium made of water and alcohol, adding a cationic polymer and then sufficiently stirring and then adding and adding a binder resin . When other additives are used, they may be added after the above-mentioned combination.

● About metal plate

The material of the metal plate is not particularly limited, and examples thereof include an aluminum plate, an iron plate, a stainless plate, and a copper plate. When the metal plate carrying the sorbent layer is used for a heat exchanger or the like, it is particularly preferable to use an aluminum plate from a high heat conductivity, light weight and low cost. The above-described method of applying the coating agent for a sorbent agent may include a method of impregnating the coating composition with a sorbent agent to effect centrifugation, a method of coating using a bar coater, a blade, or the like, or a spraying method. The coating amount is not particularly limited, but if the coating amount is too large, cracking of the sorbent layer tends to occur. On the other hand, if the coating amount is too small, it becomes difficult to form a homogeneous sorbent layer. ² , and more preferably 50 to 150 g / m ² .

● For anionic primer layer

The anionic primer layer improves the adhesion of the sorbent layer to the metal plate. That is, when the anionic primer layer is not provided on the metal plate, the wettability to the coating liquid for the sorbent agent is insufficient and uniform application is difficult. In addition, the adhesiveness between the formed sorbent layer and the metal plate is lowered.

In the case where the cationic polymer is not added to the coating solution for the sorbent agent even in the case of the metal plate having the anionic primer layer, the adhesiveness between the metal plate and the sorbent layer is significantly lowered, It is presumed that the adhesion is manifested by

The method of forming the anionic primer layer on the metal sheet is not particularly limited and a method such as coating can be employed. Here, the anionic primer applied to the metal plate is preferably applied so as to cover the entire surface of the metal plate, and the amount thereof is preferably 1 to 15 g / m ² , more preferably 2 to 10 g / m ² .

As the anionic primer for forming such an anionic primer layer, it is preferable that the anionic primer has adhesiveness to a metal plate and adhesiveness to a sorbent layer, and has water resistance and corrosion resistance. Specific examples thereof include a urethane resin, an acrylic resin, and an epoxy resin.

● About Heat Exchanger

As the heat exchanger of the present invention, for example, a heat exchanger in which a sorption material-supporting metal plate manufactured by the above method is finely processed and assembled with another member, or a heat exchanger in which a sorption agent layer is supported by the above- And the like. The shape of the heat exchanger is not particularly limited. For example, the shape of the heat exchanger is not particularly limited. For example, a rotor type obtained by winding a corrugated metal plate or a block type obtained by laminating, or a plurality of fins arranged at intervals of 0.5 to 5.0 mm And the like.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. The parts and percentages in the examples are expressed by weight unless otherwise specified. First, an evaluation method of each characteristic and a notation of the evaluation result will be described.

[Average Particle Diameter]

SALD-200V " manufactured by Shimadzu Seisakusho Co., Ltd., using water as a dispersion medium, and the average particle diameter was determined from the particle diameter distribution shown on a volumetric basis.

[Amount of carboxyl group]

1 g of a sufficiently dried sample is quenched (X [g]), 200 ml of water is added thereto, and a 1N hydrochloric acid aqueous solution is added while heating to 50 캜 to adjust the pH to 2 so that all of the carboxyl groups contained in the sample are converted into H- , And then titration curves were determined in 0.1 N NaOH aqueous solution according to the conventional method. From this titration curve, the amount of consumption of aqueous NaOH solution (Y [ml]) consumed in the H-type carboxyl group was determined, and the amount of carboxyl groups contained in the sample was calculated by the following formula.

Amount of carboxyl group [mmol / g] = 0.1 Y / X

[Saturated moisture absorption rate]

First, the saturated moisture absorptivity of the sorbent layer refers to a value obtained by the following method. A sorbent layer was formed on an aluminum plate (including a primer treatment) Wp [g] which had been previously weighed in the same manner as in Example, and the aluminum plate carrying the sorbent material was used as a test sample. The aluminum plate carrying the sorbent material was dried with a hot air drier at 120 ° C for 1 hour and weighed (Wds [g]). Then, the sample was left in a constant-temperature and humidity-controlled humidifier at a temperature of 20 ° C and a relative humidity of 65% , And the weight of the moisture-absorbing sample is measured (Wws [g]). Based on the above results, the saturated moisture absorption rate is calculated by the following formula.

Saturated moisture absorption rate (% by weight) = {(Wws-Wds) / (Wds-Wp)} 100

[Moisture absorption rate]

The measurement of the moisture absorption rate was carried out as follows. And a sorption agent layer was applied to an aluminum plate of 5 x 8 cm so as to have a coverage of 50 g / m ² to obtain a sample for moisture absorption rate. The obtained sample is dried at 120 占 폚 for 1 hour and then subjected to moisture absorption for 1 minute in a thermostatic hygrostat at 20 占 폚 and 65% RH. After drying at this time, the moisture absorption amount was measured from the difference in sample weight after moisture absorption for 1 minute.

[Remaining rate of sorbent layer due to water immersion (adhesion property of sorbent layer)] [

The residual ratio of the sorbent layer in water as an index showing the adhesion to the base material is measured as follows. The sorbent layer is carried on an aluminum plate (including a primer treatment) (Wp [g]) of 5 x 8 cm in size so as to have a coating amount of 50 g / m ² , dried at 120 ° C for 1 hour, [g]). The thus obtained aluminum plate was immersed in a water bath at 50 占 폚 for 1 hour and then dried at 120 占 폚 for 1 hour. This operation was repeated five times and the dry weight was measured (Wds2 [g] ). Based on the above results, the residual ratio is calculated by the following equation.

Remaining rate (%) = {(Wds2-Wp) / (Wds1-Wp)} 100

This value is a numerical value showing the water resistance of the aluminum plate supporting the sorbent material. If this value is large, it can be judged that the water resistance is high. In addition, the surface state of the sorbent layer before and after the test was visually evaluated according to the following criteria, and water resistance was evaluated comprehensively including the shape-retaining property of the sorbent layer.

◎: No breakage

○: Almost no cracks

△: There is a little crack

X: Highly broken

[Production of particles of organic polymer-based sorbent agent]

A monomer mixture composed of 55 parts of acrylonitrile, 10 parts of methyl acrylate and 35 parts of divinylbenzene was added to 300 parts of an aqueous solution containing 0.5 parts of ammonium persulfate, and then 0.6 parts of sodium pyruvate was added thereto. The mixture was polymerized at 65 DEG C for 2 hours. 15 parts of the obtained particles were dispersed in 85 parts of water, to which 10 parts of sodium hydroxide was added, followed by hydrolysis reaction at 90 占 폚 for 2 hours, followed by washing, dehydration and drying to obtain organic polymer-based sorbent particles. The particle had a degree of crosslinking of 19, an average particle diameter of 30 mu m, and a carboxyl group amount of 6.3 mmol / g.

[Example 1]

130 parts by weight of water and 127 parts by weight of ethanol are added to 100 parts by weight of the organic polymer-based sorbent agent particles dried at 120 DEG C for 16 hours or more and stirred. 33 parts by weight of an aqueous dispersion type urethane resin "SUPERFLEX 620" (solid content 30%, Daiichi Kyo Gijyaku Co., Ltd.) as a cationic polymer was added to the mixed solution, and the mixture was stirred for one hour. To this was added 77 parts by weight of an aqueous dispersion type neutral urethane resin "Superflex E-2000" (solid content: 50%, glass transition point -38 캜, manufactured by Daiichi Kyoe Seiyaku Co., Ltd.) diluted to 40% solids, To obtain a coating solution. The proportion of water in the coating liquid was 200 parts by weight based on 100 parts by weight of the organic polymer-based sorbent agent particles.

Subsequently, the aluminum plate was coated with an anionic urethane resin, Superflex 170 (manufactured by Daiichi Kyo Gijyaku Co., Ltd.) as an anionic primer so as to have a supported amount of 5 g / m ² .

The aluminum plate was coated with the sorptive agent coating solution so as to have the coating amount shown in Table 1 using a bar coater. After the application, preliminary drying was performed at room temperature, and then drying was carried out at 120 ° C for 1 hour to obtain an aluminum plate supporting the sorbent material. Table 1 shows the evaluation results of the obtained aluminum plate having the sorbent agent. As can be seen from Table 1, in the obtained aluminum plate supporting the sorbent agent, the sorbent layer cracked little and had a good surface state even after the water immersion test.

[Example 2]

105 parts by weight of water and 168 parts by weight of ethanol were added to 100 parts by weight of the organic polymer-based sorbent agent particles dried at 120 DEG C for 16 hours or more and stirred. 34 parts by weight of water dispersible urethane resin "Superplex 620" (solid content 30%, manufactured by Daiichi Kyoei Co., Ltd.) as a cationic polymer was added to the mixture, and the mixture was stirred for 1 hour. To this was added 75 parts by weight of an aqueous dispersion type neutral urethane resin "Superplex E-2000" (solid content 50%, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) diluted with 40% solids, and then 10% aqueous polyvinyl alcohol solution And sufficiently stirred to obtain a coating liquid. An aluminum plate carrying a sorbent material was produced in the same manner as in Example 1, using the obtained coating liquid. As shown in Table 1, the obtained aluminum plate supporting the sorbent material exhibited high adhesiveness as in Example 1 and had a good surface state even after the water immersion test. Further, in Example 2, the surface state was better than that of Example 1 even in a low deposition amount of application amount of 25 / m ² , and high film-forming property was obtained.

[Example 3]

99 parts by weight of water and 160 parts by weight of ethanol are added to 100 parts by weight of organic polymeric sorbent agent particles dried at 120 DEG C for 16 hours or more and stirred. 67 parts by weight of a 15% polyallylamine aqueous solution was added to the mixed solution and stirred for 1 hour. To this was added 75 parts by weight of an aqueous dispersion type neutral urethane resin "Superplex E-2000" (solid content: 50%, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) diluted with 40% solids, and sufficiently stirred to obtain a coating liquid. An aluminum plate carrying a sorbent material was produced in the same manner as in Example 1, using the obtained coating liquid. As shown in Table 1, the obtained sorptive agent-carrying aluminum sheet had almost no breakage of the sorptive agent layer after application and drying as in Examples 1 and 2, and did not cause separation of the sorptive agent layer even when the water immersion test was repeated. When the submergence test was repeated, the sorbent layer tended to be more prone to cracking as compared with Examples 1 and 2. This was because when the water-soluble polymer, polyallylamine, was removed from the surface of the organic polymer-based sorbent particles by a water- .

[Comparative Example 1]

An aluminum plate carrying a sorbent material was produced in the same manner as in Example 1 except that the aluminum plate was not subjected to the primer treatment. As shown in Table 1, the obtained sorbent material-supporting aluminum plate had substantially the same surface state as in Example 1, but in the case where the sorbent layer was completely peeled in the water immersion test and the anionic primer treatment was not carried out, .

[Comparative Example 2]

155 parts by weight of water and 135 parts by weight of ethanol were added to 100 parts by weight of the organic polymer-based sorbent agent particles dried at 120 DEG C for 16 hours or more and stirred. To this mixture was added 75 parts by weight of an aqueous dispersion type neutral urethane resin "Superplex E-2000" (solid content: 50%, manufactured by Daiichi Kyo Gijyaku Co., Ltd.) diluted with 40% solids to obtain a coating solution. As in Example 1, the proportion of water in the coating liquid was 200 parts by weight based on 100 parts by weight of the organic polymer-based sorbent agent particles. An aluminum plate carrying a sorbent material was prepared in accordance with Example 1 using the obtained coating liquid. As shown in Table 1, since the sorptive agent-supported aluminum plate obtained in Comparative Example 2 did not use the cationic polymer, many cracks of the sorptive agent layer in the drying process were observed. Further, by repeating the submergence test, the sorption agent layer was further withdrawn, and the removal from the substrate was observed.

[Comparative Example 3]

130 parts by weight of water and 103 parts by weight of ethanol were added to 100 parts by weight of the organic polymer-based sorbent agent particles dried at 120 DEG C for 16 hours or more and stirred. To this was added 100 parts by weight of an aqueous dispersion type urethane resin "Superflex 620" (solid content 30%, Daiichi Kyo Gijyaku Co., Ltd.) as a cationic polymer, and the mixture was stirred for 1 hour to obtain a coating liquid. An aluminum plate carrying a sorbent material was prepared in accordance with Example 1 using the obtained coating liquid. As shown in Table 1, the surface of the sorptive agent layer at the time of application and drying was good in the sorptive agent-retained aluminum sheet obtained in Comparative Example 3, but from the sorptive agent layer, Disappearance of the sorbent particle was observed. It is considered that this is because the binder resin is not added and the force of bonding the organic polymer-based sorbent particles to each other is weak only with the cationic polymer.

Claims (7)

An organic polymer-based sorbent particle comprising a carboxyl group and an organic polymer having a crosslinked structure, a cationic polymer adhered to the surface of the sorptive agent, a binder resin, an alcohol and water. The sorptive coating composition according to claim 1, which contains 100 to 500 parts by weight of water based on 100 parts by weight of the organic polymer-based sorptive. The sorptive coating composition according to claim 1 or 2, wherein the cationic polymer is a cationic urethane resin. The sorptive coating composition according to any one of claims 1 to 3, wherein the binder resin is a neutral urethane resin or a weakly anionic urethane resin. The sorptive coating composition according to any one of claims 1 to 4, which contains polyvinyl alcohol. A sorption agent-bearing metal sheet having a sorption agent layer formed by coating the sorption agent coating solution according to any one of claims 1 to 5 on a metal sheet and characterized by having an anionic primer layer between the sorption agent layer and the metal sheet And a metal plate supporting the sorbent material. A heat exchanger having the sorptive material-carrying metal plate according to claim 6.