JP2002355916A - Hydrophilic material, hydrophilic member, method for manufacturing them, and hydrophilic coating agent set - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrophilic material obtained by forming a water film on the surface of a film having anti-stick quality developing anti-fogging capacity and also having damage resistance, chemical washing properties, anti-fogging capacity, good appearance, high temperature/high humidity resistance or the like. SOLUTION: The hydrophilic material or member having high damage resistance and provided with both of anti-stick quality and anti-fogging properties good in chemical washing properties, anti-fogging capacity, high temperature/ high humidity resistance, appearance or the like can be formed by forming a film having a two-layered or three-layered coating structure, consisting of an upper layer having anti-stick quality comprising a combination of a hydrophilic inorganic oxide, a carboxylic acid-containing compound and metal ions, and a first film as a lower layer obtained only from a water absorbable organic polymer or a combination thereof with an inorganic binder and metal ions.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrophilic material (including a functional material having a function of preventing fogging, that is, a function of preventing water droplets from adhering to water, in addition to a function of preventing fogging) and a hydrophilic member. And a method for producing the same and a hydrophilic coating agent set.

[0002]

2. Description of the Related Art With respect to mirrors used in water-filled spaces, for example, mirrors placed in bathrooms and lavatories often experience fogging due to steam of hot water adhering to the surface and often lose visibility of reflected images. Is Rukoto.

As one method for solving this problem, a method of removing fogging by heating the mirror to prevent fogging of the mirror surface by setting the surface temperature of the mirror itself to a dew point or higher has been conventionally known.

As another method for solving this problem, there is disclosed a method in which a mirror surface is coated with a water-absorbing coating composition and a film having a moisture absorbing function is provided so as to exhibit anti-fog performance. (Hereinafter, the term “moisture absorption function” in the present specification refers to, for example, when steam or hot water condensed water or water droplets adhere to the mirror surface, they are absorbed by the coating composition. This is a function of preventing the mirror surface from being clouded or overshadowed by condensed water or water droplets of moisture by preventing the mirror surface from remaining on the surface). By the way, the above-mentioned JP-A-9-113704
Include, as a water-absorbing coating composition, for example, polyacrylic acid, which is one of water-absorbing organic polymers, and a polymer having an OH group formed by hydrolysis and polycondensation of an inorganic alkoxide. Coating compositions, which further include a catalyst such as N, N-dimethylbenzylamine. The resulting film has an organic-inorganic hybrid structure, and has the property of not absorbing or peeling off even if the moisture absorbing film is saturated with moisture, as well as being characterized by water resistance. is there. Therefore, such a film is a film that can be practically used as an anti-fog film for a vanity mirror requiring water resistance.

[0005] Another method for solving this problem is as follows.
A method has been considered in which the surface of the mirror is made hydrophilic so that the surface of the mirror is easily wetted and a droplet function that suppresses the generation of water droplets is used (hereinafter, the “drop function” in the present specification includes the droplet function). When water is applied to the coated film, the water droplets spread and spread on the surface of the coated film to generate a flat water film on the coated film, and the water film absorbs surrounding moisture. To
A state in which moisture adheres as a semicircular water droplet, that is, a state in which unevenness due to water droplets can be prevented, and irregular reflection of incident light such as sunlight on the surface of the film is prevented, and the film does not become cloudy). Examples of the method include a method in which a surfactant is applied to the surface of a base material to impart hydrophilicity,
There is a method of imparting hydrophilicity by coating a film containing metal oxide fine particles having a particle size of 00 nm on a substrate.

[0006] As an example of a hydrophilization technique using a film of an organic substance or a dropping technique, see Japanese Patent Application Laid-Open No. 6-10 / 1994.
7967, a hydrophilic polymer portion formed from N-methylol (meth) acrylamide, a predetermined (meth) acrylamide compound and a lower alkyl (meth) acrylate, and a functional group such as a sulfonic acid group and a carboxyl group. And a hydrophobic polymer portion formed from a copolymerizable vinyl-type monomer and a copolymerizable lower alkyl (meth) acrylate.
Antifogging agent composition comprising a block or graft copolymer consisting of two polymer parts, wherein the weight ratio of the hydrophilic polymer part to the hydrophobic polymer part is 50/50 to 95/5 A method has been considered in which an object is applied to a base material to impart drip properties.

[0007]

However, in the method of removing the fogging by heating to prevent the fogging of the mirror surface by setting the surface temperature of the mirror itself to be higher than the dew point, a power source is required, and consideration is given to waterproofness and the like. There is a problem that the installation method is required, the use range is naturally limited, and the heating wire is required, so that the cost is high.

[0008] In a method in which a mirror surface is coated with a water-absorbing coating composition and a film having a moisture-absorbing function is provided to exhibit anti-fog performance, for example, when the mirror is installed in a bathroom, the mirror during bathing may be used. Under a high humidity environment, the composition immediately fogged, and there was a problem that the composition fogged in a short time, which was almost the same as that of a mirror to which the composition was not applied. Therefore, the anti-fog technology cannot be used in a high humidity environment such as a bathroom.

In the method of imparting hydrophilicity by applying a surfactant to the surface of a substrate, the applied surfactant is easily removed from the surface of the substrate, and the surfactant is repeatedly applied each time. If not, there would be a problem that the effect would not last.

The method of imparting hydrophilicity by coating a film containing metal oxide fine particles having a particle diameter of 4 to 300 nm on a substrate is referred to as having a particle diameter of 4 to 300 nm. A film having metal oxide fine particles as a matrix is coated on a substrate, and the surface of the film has an arithmetic average roughness (Ra) of 1.5 to 80 nm and an average interval of unevenness (Sm).
Is a method in which the surface of the coating film has a dropping function by forming irregularities having a thickness of 4 to 300 nm. In this method, as long as water is applied to the coating surface, the antifogging performance is maintained for many hours even in an environment where the humidity is high and the fogging is likely to occur. There are no features. However, this method is 100% at 40 ° C.
In such a high-temperature, high-humidity environment, the antifogging performance deteriorates in one day, and the film surface becomes hydrophobic and repels.

Further, this method is intended to improve hydrophilicity, so that shampoos and rinses having hydrophilic properties,
It has a strong adsorbing power even for detergents that are always used in bathrooms such as soap, and it is difficult to remove once it adheres, causing the problem of dropping performance of the coating and repelling water. I have.

In addition, the method of applying the anti-fogging agent composition using the block or graft copolymer and exhibiting the drip function has an advantage that the anti-fogging property can be exhibited in a high humidity environment such as a bathroom. However, since there is also a problem that it is difficult to form a hard coating, when the composition is applied to a substrate such as a mirror, the surface is easily scratched, and the visibility of the mirror is reduced. There is also a disadvantage. In addition, this method has a strong adsorptive power to detergents that are constantly used in the bathroom, such as shampoos, rinses, and soaps having hydrophilic properties, and is difficult to remove once adhered to the coating. There is also a problem that the drop performance is deteriorated and water is repelled.

In view of the above circumstances, the present invention can be used in a high-humidity environment such as a bathroom, maintains excellent anti-fog performance for a long time, has excellent scratch resistance, and furthermore, can be used in a high-temperature and high-humidity environment. Even if left for a long period of time, the anti-fog performance is maintained, and even if a cleaning agent such as shampoo, rinse, or soap that is always used in the bathroom adheres to the coating surface, the drip performance of the coating can be easily recovered by washing with water etc. An object of the present invention is to provide a hydrophilic material and a hydrophilic member having chemical cleaning properties and high durability, a method for producing the hydrophilic material and a hydrophilic coating agent set.

[0014]

According to the first aspect of the present invention, there is provided a liquid crystal display device comprising: (a) a first film containing a water-absorbing organic polymer; A) a hydrophilic material comprising a second coating comprising a hydrophilic inorganic oxide and (c) a carboxylic acid-containing compound.

The feature of the hydrophilic material is that the first coating obtained from the first composition has a moisture absorbing function of absorbing moisture in the surrounding atmosphere, and is obtained by applying and curing the second composition. The surface portion to be formed has a drip function. That is, due to the presence of the surface portion, the water droplets spread on the surface of the coating film and generate a flat water film on the coating film. Excess water that does not contribute to water film formation is absorbed by the first coating portion,
Due to the synergistic effect, the anti-fog effect is exhibited even in a very humid environment such as a bathroom. Further, in the above configuration, (a) the water-absorbing organic polymer has a moisture absorbing function,
(B) The hydrophilic inorganic oxide has a role of expressing a droplet function. Therefore, the hydrophilic material is constituted by a two-layer coat film of a moisture-absorbing film in which the first film is a lower layer and a droplet coating film in which the second film is an upper layer. In the two-layer coat film, the carboxylic acid is used. It is considered that the contained compound has a role of binding the hydrophilic inorganic oxides or the hydrophilic inorganic oxide and the lower layer. further,
The carboxylic acid-containing compound has an effect of suppressing the phenomenon of deterioration of hydrophilicity under high temperature and high humidity conditions. The main cause of the deterioration is considered to be the phenomenon of weathering that occurs in glass and the like. This is because the carboxylic acid-containing compound is considered to have an effect of suppressing this weathering. By the way, this phenomenon of weathering is due to the ion exchange between hydrogen ions of water adsorbed on the silica surface and alkali ions on the silica surface. It is a phenomenon that is produced and further reacts with carbon dioxide gas in the air to form a carbonate, which shows greater corrosiveness and corrodes the entire silica. It is said that the rate of this corrosion doubles each time the pH is increased by 1 or the temperature is increased by 10 ° C., and it is considered that this corrosion spreads at a considerable speed in a high-temperature and high-humidity situation. However, in the carboxylic acid-containing compound, in the coating solution before the coating, alkali ions ion-bonded to silica and hydrogen ions in the carboxylic acid-containing compound undergo ion exchange, and the alkali ions are separated from the silica. Since the film is formed in a state where the film is formed, the formed film does not undergo weathering and becomes a coating film having a property of maintaining hydrophilicity even in a high-temperature and high-humidity condition (hereinafter referred to as high-temperature and high-humidity resistance). As described above, it is considered that the carboxylic acid-containing compound has an effect of suppressing the phenomenon of hydrophilic degradation under high temperature and high humidity conditions.

In addition, by using a hydrophilic material having such a two-layer coating film, the effect of improving the wettability of water by the surface of the droplet coating film as described above, in other words, reducing the contact angle of water droplets. An effect is added, and a water film can be generated by scratching the film with water. for that reason,
As compared with an antifogging film having only a moisture absorbing film in which the antifogging performance does not last for a long time, there is an effect that a film having a characteristic that the antifogging performance lasts for a long time can be formed. Then, the hydrophilic material which is the coating is applied to a base material such as a mirror or a film to form a hydrophilic member, and the member is attached to, for example, a bathroom mirror or the like in a high humidity environment, thereby forming the bathroom. It is possible to create a mirror exhibiting anti-fog performance suitable for a mirror or the like.

In the invention according to claim 2, which has been made to solve the above-mentioned problem, (a) a water-absorbing organic polymer and (b) a hydrophilic inorganic oxide are provided between the first coating and the second coating. (C) A hydrophilic material comprising at least a carboxylic acid-containing compound and having a third coating interposed therebetween.

In the present invention, at least (a) a water-absorbing organic polymer, (b) a hydrophilic inorganic oxide, and (c) a carboxylic acid-containing compound are contained between the first coating and the second coating. By providing a hydrophilic material characterized by having a third coating interposed, the hydrophilic material can be an upper first coating, a lower second coating, or an intermediate layer between the upper and lower layers. Although the composition of the three-layer coat film in which there are three layers of the third film will be present, the components of the first film and the components between the second films are mixed with each other to form the third film,
Since the third coating is present between the first and second coatings, the bonding strength between the individual components of the two coatings is increased, unlike the above-described configuration in which the second coating is merely placed on the first coating. In addition, there is a feature that the adhesion between the coatings is improved. Therefore, for example, even when sliding a shampoo moistened with water against the surface of the coating, deterioration of the droplet function is suppressed, and an effect of obtaining a hydrophilic material having improved water resistance or scratch resistance is obtained. There is.

According to a third aspect of the present invention, there is provided a hydrophilic material, wherein the first coating and / or the third coating further comprises an inorganic binder. I will provide a. In the present invention, by providing a hydrophilic material characterized by further containing an inorganic binder in the first coating and / or the third coating, the inorganic binder-containing first coating obtained thereby is obtained. One coating and / or a hydrophilic material having a third coating has a structure having an organic-inorganic hybrid structure, compared to the first coating or the third coating composed of only the organic substance as described above, It becomes a film having a high film surface strength and has an effect of obtaining a hydrophilic material having improved water resistance or scratch resistance.

Further, since the hydrophilic material has a high surface strength of the coating, shampoo, rinsing, etc. may be applied to the surface of the coating.
Even if there is a deposit which cannot be removed only by applying water or hot water, it is possible to wipe off with a hand or a towel without worrying about the damage of the coating and the deterioration of the performance to some extent.

The hydrophilic material forms a two-layer coating film or a three-layer coating film, and the first film is the upper layer, the second film is the lower layer, or the third layer is the intermediate layer between the upper and lower layers. Although it becomes a configuration of the coating, the upper second coating develops dropletity for the reasons described above, but the lower first coating is
It is mainly composed of a water-absorbing organic polymer capable of absorbing moisture in the surrounding atmosphere, and an inorganic binder serving as a spacer for preventing bonding between polymers or adhesion between polymers. By adopting such an organic-inorganic hybrid structure, even when water is absorbed in the coating, the coating is characterized by being able to obtain a coating having water resistance or scratch resistance without causing the coating to dissolve or break easily. is there. In addition, since the binder can be used as a spacer, for example, it prevents hydrogen bonding due to the proximity of hydroxyl groups in the water-absorbing organic polymer, and provides voids so that water and moisture easily enter the coating. The feature is that the scratch resistance can be increased without lowering the moisture absorption performance. Therefore, when a two-layer or three-layer coat film is formed with the film having such a configuration as a lower layer, the film is hygroscopic or
It is possible to obtain a coating film having both the dripping property and the scratch resistance.

Therefore, the two-layer coating film or the three-layer coating film has a drip property that keeps the anti-fog performance for a long time,
The surface strength of the coating, i.e., at the same time as the scratch resistance is increased, as described above, even when a chemical such as shampoo, rinse, or conditioner usually used in a bathroom or the like adheres to the coating surface, water for the chemical, Alternatively, there is a feature that a hydrophilic material having high chemical cleaning performance, which can be easily washed off by washing with a neutral detergent or simple hand washing with water, can be obtained.

According to a fourth aspect of the present invention, there is provided a hydrophilic material, wherein the inorganic binder is a zirconium compound.
In the present invention, since the inorganic binder is a zirconium compound, the coating liquid used for forming the first coating or the third coating has a lower consumption than a silicon compound as another inorganic binder. There is an effect that a coating liquid having a high foaming performance can be prepared. For this reason, zirconium compounds often have the ability as a binder even without a hydrophobic functional group such as an alkoxy group, and in the case where air enters the coating liquid containing the zirconium compound. However, there is a surface where the problem that air is trapped and it is difficult to remove bubbles from the coating liquid does not easily occur. Conversely, in the case of an inorganic binder of the silicon compound, air is trapped in the hydrophobic groups of the silicon compound, and particularly in the case of a liquid having a high viscosity, it becomes difficult to remove air bubbles from the coating liquid, and as a result, To the coating machine,
When the hydrophilic material is mass-produced, there is a high possibility that a problem that the coating contains air bubbles can be increased. As described above, the zirconium compound has an effect that a coating liquid having high defoaming performance can be prepared.

According to a fifth aspect of the present invention, there is provided a hydrophilic material, wherein the zirconium compound is zirconium oxynitrate. In the present invention, the zirconium compound is
By using zirconium oxynitrate, it is possible to prepare a coating agent having less defects such as metal corrosion than other zirconium compounds such as zirconium oxychloride. Then, even if this liquid is coated on a base material such as glass by a coating machine to create a hydrophilic material, there are few problems such as corrosion of the coating machine piping by the liquid, and the life of the coating machine is reduced. There is an effect that can be lengthened.

According to a sixth aspect of the present invention, there is provided a hydrophilic material, wherein the water-absorbing organic polymer is polyvinyl alcohol. In the present invention, since the water-absorbing organic polymer is polyvinyl alcohol, there is an effect that a first coating having particularly high water resistance can be obtained as compared with other water-absorbing organic polymers. The term “water resistance” as used herein refers to the performance of a coating that does not reduce the coating strength even when a liquid such as water contacts the first coating and is absorbed by the coating. For example, when a mirror coated with polyvinyl alcohol is immersed in water for 1 minute or more, and then taken out from the mirror, and the surface of the coating is touched with a hand, a phenomenon that the coating is easily peeled off is observed. On the other hand, a film formed by combining polyvinyl alcohol and the above-mentioned zirconium compound hardly peels off even when the above evaluation is performed, and a film having a high film strength can be obtained. The fact that the film strength of the film does not decrease even in the state of absorbing water in this way is referred to as improved water resistance of the film. And, since polyvinyl alcohol has higher water resistance than the water-absorbing organic polymer such as polyethylene oxide, the coating itself obtained by itself,
It is believed that the resulting hydrophilic material can be made more water-resistant than the others.

According to a seventh aspect of the present invention, the hydrophilic inorganic oxide is in the form of fine particles, and the mode of the particle diameter is 4 to 300 nm. Provide a hydrophilic material. In the present invention, the hydrophilic inorganic oxide is in the form of fine particles, and the mode of the particle diameter is 4 to 300 nm. This has the effect of producing a hydrophilic material that does not impair the appearance. The reason is that the mode of the particle size of the hydrophilic inorganic oxide is 4
When the one having a thickness of not more than nm is used, there is a problem that the wettability of the surface of the coating film is deteriorated and the droplet performance is not exhibited. In addition, when the mode of the particle diameter is 300 nm or more,
Since it is considered that a problem that the coating may become cloudy and the transparency may be lost occurs, in this case, it is considered that the condition of the particle diameter as described above is preferable.

[0027] In order to solve the above-mentioned problem, the invention according to claim 8 provides a hydrophilic material, wherein the hydrophilic inorganic oxide is silica and / or alumina. In the present invention, since the hydrophilic inorganic oxide is silica and / or alumina, there is an effect that a hydrophilic material having both a scratch resistance and a high temperature and high humidity resistance and having a dropping function can be produced. This phenomenon is remarkably different from the case where silica or alumina is used alone. The reason for this is that silica is a material that has a higher binding ability to the first coating than other hydrophilic inorganic oxides and can be made of a hydrophilic material having high scratch resistance, but has a poor surface resistance to high temperature and high humidity. is there. However, the combination with the carboxylic acid-containing compound has a feature that the high-temperature and high-humidity resistance is improved. On the other hand, although alumina has high resistance to high temperature and high humidity, it alone has a small bonding ability with the first coating and has a weak scratch resistance. However, in combination with the carboxylic acid-containing compound, not only the high-temperature and high-humidity resistance is improved, but also the bonding ability with the first coating is increased, and the scratch resistance is improved. And, since the coating film which combines these two oxides has both of these functions, it becomes a coating film having a dropping function having both higher scratch resistance and high temperature and humidity resistance. As described above, since the hydrophilic inorganic oxide is silica and / or alumina, there is a feature that a coating film having a dropping function having both scratch resistance and high temperature and high humidity resistance is obtained.

According to a ninth aspect of the present invention, there is provided a hydrophilic material, wherein the carboxylic acid-containing compound is citric acid and / or tartaric acid. In the present invention, the carboxylic acid-containing compound is citric acid and / or tartaric acid,
The binding ability between silica or a hydrophilic functional group such as a hydroxyl group present in a silica and a lower layer constituent material has an effect of being higher than other carboxylic acid-containing compounds, and has an effect of increasing the scratch resistance of the hydrophilic material. This has the effect of improving the performance. The reason is that citric acid and tartaric acid have a hydroxyl group in addition to the carboxyl group, and this hydroxyl group is considered to be a dehydration-condensation reaction between the hydroxyl groups between the silica-containing hydroxyl group and other substances, and to be bonded. Can be And since this bonding force is stronger than the bonding force between the carboxyl group and the silica-containing hydroxyl group, the carboxylic acid-containing compound having as many hydroxyl groups as possible binds the silica or the silica and the first coating. It is believed that the material has improved ability, and as a result, is a preferable material in the scratch resistance of the hydrophilic material. Therefore, citric acid having one hydroxyl group and tartaric acid having two hydroxyl groups are considered to be preferable materials for the scratch resistance of the hydrophilic material.

In the invention according to claim 10 which has been made to solve the above-mentioned problem, the first coating is such that the zirconium compound is in a ratio of 50 to 150 parts by weight with respect to 100 parts by weight of the water-absorbing organic polymer. Provide a hydrophilic material characterized by being present. In the present invention, by providing a hydrophilic material characterized in that the zirconium compound is present in a proportion of 50 to 150 parts by weight with respect to 100 parts by weight of the water-absorbing organic polymer in the first coating. In addition, it is possible to improve the scratch resistance and maintain the water film for a long time in relation to the expression of the droplet performance. For example, the hydrophilic material prepared by mixing the zirconium compound in a proportion of 50 parts by weight or less with respect to 100 parts by weight of the water-absorbing organic polymer is coated with water to form a water film on the film. But 1 ~
A phenomenon in which the water film disappears in two minutes is observed. Then, when rubbed with a foam or the like, a phenomenon in which the dropping property deteriorates is observed. Further, in the case of a hydrophilic material prepared by mixing the zirconium compound in a proportion of at least 150 parts by weight with respect to 100 parts by weight of the water-absorbing organic polymer, there is a risk that the coating may crack in the coating. . As described above, the zirconium compound is mixed at a ratio of 50 to 150 parts by weight with respect to 100 parts by weight of the water-absorbing organic polymer. A film having good properties and good appearance.

According to an eleventh aspect of the present invention, there is provided a hydrophilic material, wherein the first coating further comprises a hydroxyl group-containing organic compound. In the present invention, by providing a hydrophilic material characterized in that the first coating further contains a hydroxyl group-containing organic compound, the adhesion between the first coating and the second coating can be improved. As a reason for this, for example, tartaric acid, which is one of the hydroxyl group-containing organic compounds, is present in the first coating, so that the hydroxyl groups present in the tartaric acid have a zirconia compound or polyvinyl alcohol in the first coating, A dehydration-condensation reaction is performed between silica and a hydrophilic inorganic oxide of alumina in the second coating, and the first coating and the second coating are bonded to increase the adhesion between the two coatings. Because there is.

According to a twelfth aspect of the present invention, there is provided a hydrophilic material, wherein the hydroxyl-containing organic compound is citric acid and / or tartaric acid. In the present invention, when the hydroxyl group-containing organic compound is citric acid and / or tartaric acid, the adhesion between the first coating and the second coating is further improved as compared with other hydroxyl group-containing organic compounds. The reason for this will become clear by comparing malic acid, one of the hydroxyl group-containing organic compounds, with citric acid or tartaric acid. For example,
Malic acid has three hydroxyl groups including the hydroxyl group in the carboxyl group, while citric acid or tartaric acid has four hydroxyl groups including the hydroxyl group in the carboxyl group. Therefore, the latter is easier to carry out a condensation reaction with a hydroxyl group of a component of a hydrophilic material such as a zirconia compound, a water-absorbing organic polymer, or a hydrophilic inorganic oxide than the former, and a bond is formed between each component. There is an effect of increasing the adhesiveness between the first coating and the second coating containing them as constituents. Therefore, when the hydroxyl group-containing organic compound is citric acid and / or tartaric acid, the adhesion between the first coating and the second coating is further improved as compared with other hydroxyl group-containing organic compounds.

According to a thirteenth aspect of the present invention, there is provided a hydrophilic material, wherein the first coating and / or the third coating further include a first metal ion. I do. In the present invention, since the first coating and / or the third coating further contain the first metal ion, there is an effect that a hydrophilic agent having improved chemical detergency can be obtained. Here, the first metal ion refers to all metal ions having a positive charge, and examples thereof include a typical metal element such as an alkali metal and a metal ion such as a transition metal element. The reason may be as follows. Usually, the first coating has hydroxyl groups originating from polyvinyl alcohol and the like, and is bonded to the hydroxyl groups of the silica of the second coating by a dehydration condensation reaction, but there are also a number of unreacted hydroxyl groups that are not bonded therein. It seems to be doing. And, in the environment such as a bathroom, the hydroxyl group easily generates a metal soap, which adheres to the coating, and the adhered portion repels water. It loses the drip function of the hydrophilic material. By the way, the metal soap referred to here is soap, shampoo, and dirt that occurs in an environment such as a bathroom mirror or wall, which is a place where ionic surfactant-containing cleaning agents such as rinse are frequently used. It is a mixture formed by ionic bonding of divalent or trivalent metal ions such as calcium ions in tap water, ionic surfactants, and other sebum stains. However, when an appropriate amount of the first metal ion is mixed in advance in the first coating, a matrix is formed by ionic bonding between the hydroxyl group in the first coating and the first metal ion, and the matrix is formed in tap water. The penetration of metal ions into the first coating and the ionic bonding thereof are prevented, and as a result, the adhesion of dirt to the coating due to shampoos, soaps and the like including metal soaps can be prevented. Thus, it is considered that the chemical cleaning property of the coating can be improved.

The invention according to claim 14 for solving the above-mentioned problem is characterized in that the first metal ion is a monovalent metal ion. In the present invention, the first metal ion is a monovalent metal ion,
A hydrophilic material having improved chemical detergency can be obtained as compared with the case where another divalent or trivalent metal ion is used as the first metal ion. The reason is considered as follows. Usually, the first coating has a hydroxyl group caused by polyvinyl alcohol or the like and is bonded to the hydroxyl group of silica of the second coating by a dehydration condensation reaction, but there are also a large number of unreacted hydroxyl groups that are not bonded. It is considered that this hydroxyl group causes the metal soap to be produced in an environment where there is much metal soap, such as a bathroom, and loses the drip function of the film. Therefore, if an appropriate amount of a divalent metal ion such as magnesium ion is mixed into the first coating to prevent the ionic bond between the cation in the tap water and the hydroxyl group in the first coating as described above, the metal soap can be used. Effective for preventing adhesion of However, with respect to the monovalent negative charge of the hydroxyl group, the ion becomes a divalent positive charge and is electrically biased to the positive side, so it is difficult to electrically neutralize it. Even without mediation, there is a possibility that the ionic surfactant directly comes into ionic bond with the metal ion in the first coating. In other words, it may be in the same state as the adhesion of the metal soap to the coating. However, when an appropriate amount of a monovalent metal ion such as potassium ion is mixed in the first coating, the hydroxyl group in the first coating and this cation are ion-bonded and electrically neutralized, and their ionic bond is formed. Is prevented, it is possible to prevent the adhesion of dirt due to shampoos and soaps such as metal soap to the coating, and as a result,
It is considered that the chemical cleaning property of the coating is improved.

According to a fifteenth aspect of the present invention for solving the above-mentioned problem, the monovalent metal ion is a potassium ion. In the present invention, the monovalent metal ion is a potassium ion,
A hydrophilic material having further improved chemical detergency can be obtained as compared with the case where another monovalent sodium ion or lithium ion is used as the first metal ion. The reason may be as follows. As described above, the first coating is capable of maintaining the drip performance of the coating by preventing the generation of the metal soap by mixing the first metal ion, as described above, but associates the first metal ion with the coating. The ionic bond is not very strong as a bonding force, and when the coating comes into contact with a large amount of water, the first metal ion may be released from the coating, making it difficult to form a matrix having chemical cleaning properties as described above. is there. This tends to occur particularly when sodium ions or lithium ions are used as the first metal ions.
However, potassium ions are larger than sodium ions and lithium ions, and the ion exchange with sodium ions in the glass fills the voids created by the sodium ions in the glass without gaps, thereby strengthening the glass. There is. Therefore, when it is mixed into the first coating and is sandwiched in the void portion in the coating, potassium ions become difficult to come out therefrom, and even if a large amount of water is applied to the coating,
Outflow of potassium ions from the coating is suppressed, and the high chemical detergency of the ions can be maintained as it is. As a result, a film having high chemical detergency can be obtained.

According to another aspect of the present invention, there is provided a hydrophilic material, wherein the second coating and / or the third coating further include a second metal ion. I do. In the present invention, by providing a hydrophilic material characterized in that the second coating and / or the third coating further contains a second metal ion, a hydrophilic material further improved in chemical detergency can be obtained. can get. Here, the second metal ion refers to all metal ions having a positive charge, for example, a typical metal element such as an alkali metal,
Examples include metal ions such as transition metal elements. The reason is considered as follows. The second coating has a hydroxyl group caused by silica fine particles and the like, which is bonded to the hydroxyl group and the like of polyvinyl alcohol in the first coating by a dehydration condensation reaction, but also has a large number of unreacted unreacted hydroxyl groups. are doing. And this hydroxyl group forms metal soap under the environment where there is much metal soap due to divalent or trivalent metal ions in tap water such as a bathroom as described above, and the metal soap adheres. The part repels water and loses the drip function of the coating. However, when an appropriate amount of the second metal ion is previously mixed into the second coating or the third coating, the hydroxyl groups in the second coating or the third coating and the metal ions are ion-bonded to form a matrix. And, by this, the metal ions in the tap water enter the voids in the silica fine particles in the second coating,
It is considered that both of the invading ions are ion-bonded to the hydroxyl groups in the second coating, and as a result, generation of metal soap on the silica can be prevented, and chemical detergency is considered to be improved. .

In the invention according to claim 17 which has been made to solve the above problem, the second metal ion is a multivalent metal ion. In the present invention,
When the second metal ion is a multivalent metal ion, a hydrophilic material having improved high-temperature and high-humidity resistance is obtained. The term "multivalent" as used herein means that the metal ion has a plurality of charges, such as divalent or trivalent, instead of monovalent. The reason may be as follows. As a cause of deteriorating the high-temperature and high-humidity resistance, the phenomenon of weathering is considered to be a major cause as described above. However, when a magnesium ion or the like, which is a multivalent metal ion, is added to the second metal ion, a complex is formed between the metal oxides of silica or alumina or between a carboxylic acid-containing compound such as citric acid and the metal oxide. Alternatively, a complex is formed, and a film having a three-dimensional matrix is formed. At the same time, alkali metal ions such as monovalent sodium ions present in the silica in the second coating are eliminated from the second coating, and the generation of alkali salts that cause weathering is suppressed. Weathering of the coating is suppressed. Then, as a result of combining these improvement effects, it is considered that a hydrophilic material having improved high-temperature and high-humidity resistance can be obtained because the second metal ion is a multivalent metal ion.

The invention according to claim 18 for solving the above problem is characterized in that the multivalent metal ion is a magnesium ion and / or a calcium ion. In the present invention, when the multivalent metal ion is a magnesium ion and / or a calcium ion, a hydrophilic material having not only improved chemical detergency but also improved high-temperature and high-humidity resistance can be obtained. The reason may be as follows. The cause of deteriorating the high-temperature and high-humidity resistance is considered to be a phenomenon called weathering, which can be prevented by adding a divalent ion such as a magnesium ion as described above. Further, it can be prevented by aluminum ions which are trivalent metal ions. In this case, the ionic bond between aluminum ions and oxygen is smaller than the ionic bond between magnesium ions or calcium ions and oxygen. It is small and easily released from the coating film as compared with magnesium ions and the like. Therefore, the film made of aluminum ion,
The number of hydroxyl groups that do not have ionic bonds increases, making it easier for ionic surfactants to bond with ionic surfactants than coatings made of magnesium ions, etc. . As a result, it is considered that the obtained coating film does not deteriorate in high-temperature and high-humidity resistance, but has a tendency to slightly decrease in chemical cleaning property. By the way, the term "ionic bond property" as used herein refers to the magnitude of the ionic bond attracted to each other when two atoms are chemically bonded, calculated from the difference in electronegativity of the elements. O is 70% and 75% respectively, while Al and O are
60%. For this reason, the metal ion-added coating such as the magnesium ion is a hydrophilic material having not only high resistance to high temperature and high humidity but also improved chemical cleaning properties as compared with a coating made of aluminum ions.

The invention according to claim 19, which has been made to solve the above problem, is characterized in that the contact angle of water on the surface of the hydrophilic material is 35 degrees or less. In the present invention, when the contact angle of water on the hydrophilic surface is 35 degrees or less, there is an effect that the hydrophilic material having the surface of the hydrophilic material has a dropping function.

According to a twentieth aspect of the present invention, a contact angle on the surface of the hydrophilic material is 10 degrees or less. In the present invention, since the contact angle of water on the surface of the hydrophilic material is 10 degrees or less, an operation of applying water necessary for developing a water film on a film having a drip function is applied to the film. The effect of imparting anti-fogging property to the hydrophilic material is obtained without performing. Further, in this case, there is an effect that the antifogging performance is maintained for a long time as compared with the case of only the moisture absorbing film.

According to a twenty-first aspect of the present invention, there is provided a hydrophilic material, wherein the hydrophilic material is an antifogging material. In the present invention,
When the hydrophilic material is an antifogging material, it is possible to provide a hydrophilic material having antifogging properties for preventing fogging of the above-mentioned glass and mirrors. The antifogging material referred to here is a material having an antifogging function having a drip function and a moisture absorbing function.

According to a twenty-second aspect of the present invention, a second coating or a third coating is formed on a surface of the first coating opposite to the second coating. To provide a hydrophilic material. In the present invention, by providing a hydrophilic material characterized by forming a second film or a third film on the surface of the first film opposite to the second film, the hydrophilic material In the first coating,
A hydrophilic material, characterized in that the surface on which the second coating or the third coating is not applied further has a second coating or a third coating having the same configuration as above, and has a double-sided hydrophilic surface. Not only can provide the hydrophilic material with a function as an adhesive, but also have a hydrophilic property, an anti-fog property, or a drip function on the surface opposite to the adhesive surface. It is possible to provide a hydrophilic material. The adhesive used here means that the adhesive is adhered to the surface of a normally standing material such as a wall, a window, a door, or a mirror, and even if the material is pressed down from the surface of the material with a certain amount of force, A material that has an adhesive property that does not cause the material to peel or fall off.

According to a twenty-third aspect of the present invention, a hydrophilic material according to any one of the first to twenty-first aspects is applied to a surface of a substrate. Provide a hydrophilic member. In the present invention, claim 1
To 21 by providing a hydrophilic member characterized in that the hydrophilic material according to any one of to 21 is applied to the surface of the substrate, such as a mirror or glass, a substrate such as a PET film as described above. There is a feature that a drip function can be provided.

According to a twenty-fourth aspect of the present invention, there is provided a hydrophilic member, wherein a first coating is formed on a surface of the substrate opposite to the first coating. provide. In the present invention, by providing a hydrophilic member characterized by forming a first coating on the surface of the substrate opposite to the first coating, the first coating of the hydrophilic member, On the side opposite to the second coating or the third coating, the first coating, the second coating or the third coating is also present, so-called hydrophilic two-layer coating on both sides of the substrate or three layers It becomes a hydrophilic member having a configuration that can provide a coat film. Thus, not only can the hydrophilic member be provided with the function as an adhesive as described above, but also the surface opposite to the bonding surface has hydrophilicity, anti-fog properties, or a drip function. It is possible to provide an improved hydrophilic member.

According to a twenty-fifth aspect of the present invention, there is provided a hydrophilic member, wherein the substrate is transparent and the obtained hydrophilic member is also transparent. In the present invention, the substrate is transparent,
The resulting hydrophilic material member is also transparent, for example, can be applied to a substrate that values transparency, such as glass, without impairing the transparency of the transparent substrate, such as a dropping function A hydrophilic member capable of imparting a function to the substrate can be provided.

According to a twenty-sixth aspect of the present invention, there is provided a hydrophilic member, wherein the hydrophilic member is an anti-fog member. In the present invention, since the hydrophilic member is an antifogging member, it is possible to provide a hydrophilic member having an antifogging property for preventing fogging of the above-mentioned glass and mirrors. The anti-fog member referred to here is
It is a hydrophilic member having anti-fogging property, and is a general term for a molded article in which a hydrophilic material having anti-fogging property existing on a base material such as glass or mirror and the base material are paired.

The invention according to claim 27, which has been made to solve the above problem, is characterized in that the hydrophilic member is a hydrophilic member for a high humidity zone in a house or a non-residential facility. In the present invention, by providing the hydrophilic member as described above, for example, a hot water supply room, a kitchen, a washroom,
It is possible to provide a hydrophilic member capable of exhibiting the above-described anti-fog properties and drip properties even in all types of high humidity zones such as bathrooms and toilets.

The invention according to claim 28, which has been made to solve the above problem, is characterized in that the high humidity zone is one of a kitchen, a washroom, a bathroom, and a toilet group. In the present invention, by providing the hydrophilic member as described above, among all kinds of high humidity zones,
In particular, in a kitchen, a washroom, a bathroom, and a toilet, it is possible to provide a hydrophilic member capable of exhibiting the above-described anti-fogging property and drip property.

The invention according to claim 29, which has been made to solve the above problem, is a coating agent for forming the hydrophilic material, wherein the first coating agent contains at least (a) a water-absorbing organic polymer. And a hydrophilic coating agent set comprising (b) a second coating agent containing at least a hydrophilic inorganic oxide and (c) a carboxylic acid-containing compound. In the present invention, a coating agent for forming the hydrophilic material,
A hydrophilic coating agent set comprising (a) a first coating agent containing at least a water-absorbing organic polymer, and (b) a second coating agent containing at least a hydrophilic inorganic oxide and (c) a carboxylic acid-containing compound. By being characterized in that, the user using the set, at any time, anywhere, as much as you like, the desired amount, the anti-fog property, the two-layer coat film that can exhibit the drip property or There is a feature that a three-layer coating film can be formed.

[0049] In the invention according to claim 30, which has been made to solve the above-mentioned problem, the first coating and / or the third coating further comprise an inorganic binder. Provide an agent set. In the present invention, an inorganic binder obtained by providing a hydrophilic coating agent set characterized in that the first coating and / or the third coating further contains an inorganic binder. The hydrophilic material having the contained first coating and / or the third coating has a structure having an organic-inorganic hybrid structure, and is compared with the first coating or the third coating composed of only the organic substance as described above. Thus, a film having a high film surface strength, water resistance or
There is an effect that a hydrophilic material having improved scratch resistance can be obtained.

Further, since the hydrophilic material has a high surface strength of the coating, shampoo, rinsing and the like are applied to the surface of the coating.
Even if there is a deposit which cannot be removed only by applying water or hot water, it is possible to wipe off with a hand or a towel without worrying about the damage of the coating and the deterioration of the performance to some extent.

According to an embodiment of the present invention, there is provided a hydrophilic coating material setting material, wherein the inorganic binder is zirconium oxynitrate. In the present invention, by providing a hydrophilic coating agent set characterized in that the inorganic binder is zirconium oxynitrate, there is a problem such as metal corrosion as compared with other inorganic binders such as silicon oxychloride. With less coating agent. Then, even if this liquid is coated on a base material such as glass by a coating machine to create a hydrophilic material, there are few problems such as corrosion of the coating machine piping by the liquid, and the life of the coating machine is reduced. There is an effect that can be lengthened.

According to an embodiment of the present invention, there is provided a hydrophilic coating agent set wherein the hydrophilic inorganic oxide is silica and / or alumina. In the present invention, by providing a hydrophilic coating agent set characterized in that the hydrophilic inorganic oxide is silica and / or alumina, it has a dropping function having both scratch resistance and high temperature and high humidity resistance. There is an effect that the user using the set can create a hydrophilic material at a desired place, in a desired amount, and in a desired amount. This phenomenon is remarkably different from the case where silica or alumina is used alone.
The reason for this is that silica is a material that has a higher binding ability to the first coating than other hydrophilic inorganic oxides and can be made of a hydrophilic material having high scratch resistance, but has a poor surface resistance to high temperature and high humidity. is there. However, the combination with the carboxylic acid-containing compound has a feature that the high-temperature and high-humidity resistance is improved. On the other hand, although alumina has high resistance to high temperature and high humidity, it alone has a small bonding ability with the first coating and has a weak scratch resistance. However, in combination with the carboxylic acid-containing compound, not only the high-temperature and high-humidity resistance is improved, but also the bonding ability with the first coating is increased, and the scratch resistance is improved. And, since the coating film combining these two oxides has both of these functions, it becomes a coating film having a dropping function having both higher scratch resistance and high temperature and humidity resistance. Thus, the hydrophilic inorganic oxide is silica and / or
Also, the use of alumina has a feature that a coating film having a dropping function having both scratch resistance and high temperature and high humidity resistance is obtained.

According to a third aspect of the present invention, there is provided a hydrophilic coating agent set, wherein the carboxylic acid-containing compound is citric acid and / or tartaric acid. In the present invention,
By using a hydrophilic coating agent set characterized in that the carboxylic acid-containing compound is citric acid and / or tartaric acid, silica such as hydroxyl groups existing in silica or in a constituent material of silica and the lower layer is used. This has the effect of increasing the binding ability with the hydrophilic functional group as compared with other carboxylic acid-containing compounds, and has the effect of improving the scratch resistance of the hydrophilic material. Then, there is an effect that the user using the set can create a hydrophilic material having the above-described characteristics at a desired time, in a desired amount, and in a desired amount.

The invention according to claim 34, which has been made to solve the above problem, is characterized in that the pH of the first coating agent is 1.5 or more and 4 or less. In the present invention, by setting the pH of the first coating agent to 1.5 or more, the discoloration of the resulting hydrophilic material film is less likely to occur than in the case where the pH is less than 1.5, and the transparency of the film is reduced. And the effect of improving the film surface strength can be obtained. This effect is remarkable when a material such as zirconium oxynitrate or zirconium oxysulfate, which easily causes discoloration of the coating, is used. When the pH of the first coating agent is set to 4 or more, the viscosity of the coating agent becomes considerably high.
The pH is preferably 4 or less.

The invention according to claim 35, which has been made to solve the above problem, is characterized in that when the pH of the first coating agent is adjusted to 1.5 or more and 4 or less, an anion exchange resin is used. I do. In the present invention, when the pH of the first coating agent is adjusted to 1.5 or more, by using an anion exchange resin, compared with the method of adjusting pH by adding an aqueous alkali solution such as ammonia water, the second coating agent is used. Since the pH can be adjusted without generating a salt such as ammonium nitrate in one coating agent, there is no concern that the salt is generated in the coating agent to lower the film surface strength, and the pH is adjusted. There is an effect that can be.

In the invention according to claim 36, which has been made to solve the above-mentioned problem, the first coating agent contains the zirconium compound in a proportion of 50 to 150 parts by weight based on 100 parts by weight of the water-absorbing organic polymer. The present invention provides a hydrophilic coating agent set, characterized by being present in: In the present invention, the first coating provides a hydrophilic coating agent set, wherein the zirconium compound is present in a proportion of 50 to 150 parts by weight with respect to 100 parts by weight of the water-absorbing organic polymer. By doing so, the coating of the hydrophilic agent thus obtained can improve the scratch resistance and maintain the water film for a long time in relation to the development of the droplet performance. For example, the hydrophilic material prepared by mixing the zirconium compound in a proportion of 50 parts by weight or less with respect to 100 parts by weight of the water-absorbing organic polymer is coated with water to form a water film on the film. However, a phenomenon in which the water film disappears in one to two minutes is observed. And if you rub it with a phone etc.,
A phenomenon in which the dripping property deteriorates is observed. Further, in the case of a hydrophilic material prepared by mixing the zirconium compound in a proportion of at least 150 parts by weight with respect to 100 parts by weight of the water-absorbing organic polymer, there is a risk that the coating may crack in the coating. . As described above, the zirconium compound is mixed at a ratio of 50 to 150 parts by weight with respect to 100 parts by weight of the water-absorbing organic polymer. This is the most preferable film having a property.

According to an embodiment of the present invention, there is provided a hydrophilic coating agent set, wherein the first coating agent further comprises a hydroxyl group-containing organic compound. In the present invention, the first coating agent is further provided with a hydrophilic coating agent set characterized by containing a hydroxyl group-containing organic compound. The adhesion of the coating can be improved. As a reason for this, for example, in the case of tartaric acid, which is one of the hydroxyl group-containing organic compounds, due to its presence in the first coating, the hydroxyl group present in tartaric acid causes the zirconia compound in the first coating or A condensation reaction is performed between polyvinyl alcohol and a hydrophilic inorganic oxide of silica or alumina in the second coating, whereby the first coating and the second coating are bonded, and the adhesion between the two coatings This is because it has the effect of raising

According to an embodiment of the present invention, there is provided a hydrophilic coating agent set wherein the hydroxyl-containing organic compound is citric acid and / or tartaric acid. In the present invention, since the hydroxyl group-containing organic compound is citric acid and / or tartaric acid, the adhesion between the first coating and the second coating of the hydrophilic material obtained by the method is smaller than that of the other hydroxyl group-containing organic compounds. There is a feature that the property is further improved. The reason for this will become clear by comparing malic acid, one of the hydroxyl group-containing organic compounds, with citric acid or tartaric acid. For example, malic acid has three hydroxyl groups including a hydroxyl group in a carboxyl group, while citric acid or tartaric acid has four hydroxyl groups including a hydroxyl group in a carboxyl group. Therefore, the latter is easier to carry out a condensation reaction with a hydroxyl group of a component of a hydrophilic material such as a zirconia compound, a water-absorbing organic polymer, or a hydrophilic inorganic oxide than the former, and a bond is formed between each component. There is an effect of increasing the adhesiveness between the first coating and the second coating containing them as constituents. Therefore, when the hydroxyl group-containing organic compound is citric acid and / or tartaric acid, the adhesion between the first coating and the second coating is further improved as compared with other hydroxyl group-containing organic compounds.

According to a thirty-ninth aspect of the present invention, there is provided a hydrophilic coating agent set, wherein the first coating agent further comprises a first metal ion. In the present invention,
By providing a hydrophilic coating agent set characterized in that the first coating agent further contains a first metal ion, there is an effect of improving the chemical detergency of the hydrophilic material obtained thereby.

According to an embodiment of the present invention, there is provided a hydrophilic coating agent set, wherein the second coating agent further comprises a second metal ion. In the present invention,
By providing a hydrophilic coating agent set characterized in that the second coating agent further contains a second metal ion, there is an effect of further improving the chemical detergency of the hydrophilic material obtained thereby. .

BEST MODE FOR CARRYING OUT THE INVENTION

SUMMARY OF THE INVENTION The present invention relates to a hydrophilic material (including a functional material having a function of preventing adhesion of water droplets and a function of flowing droplets in addition to a function of preventing fogging), a hydrophilic member, and a method of manufacturing the same. And a hydrophilic coating agent set. As used herein, the term “hydrophilic material” refers to a part or all of a material such as a material surface including a functional material having a function of preventing adhesion of water droplets and a function of flowing droplets, in addition to the fogging prevention function as described above. The term "hydrophilic member" refers to a member in which a hydrophilic material is applied to a base material such as glass or plastic, and is a collective term for all the hydrophilic molded products obtained thereby. In addition, the hydrophilic material is applied to the base material referred to herein, or the base material is coated with the hydrophilic material,
By being impregnated, it means that the substrate and the hydrophilic material are integrally operated to exhibit a function such as a drip function.

The hydrophilic material of the present invention has the function of preventing fogging,
It is a film that has the function of preventing the attachment of water drops and the function of flowing water drops.
(A) a first coating comprising a water-absorbing organic polymer, and a second coating comprising (b) a hydrophilic inorganic oxide and (c) a carboxylic acid-containing compound on the first coating. And one hydrophilic material having a two-layer coating film, and between the first film and the second film, (a) a water-absorbing organic polymer, (b) a hydrophilic inorganic oxide, c) There are two types of hydrophilic material coatings comprising one hydrophilic material having a three-layer coating film characterized by interposing a third film, comprising at least a carboxylic acid-containing compound. In addition, a hydrophilic material characterized in that a second coating or a third coating is formed on a surface of the first coating opposite to the second coating, and a hydrophilic material having nothing on the contrary. There are two types of construction of the material, which means that only hydrophilic materials All four types of configurations exist.
The four types include one configuration of the first coating and the second coating,
The first coating, the second coating, and the third coating have one configuration, the first coating has one second coating on both surfaces, and the first coating has the second coating and the third coating on both surfaces. Are present one by one in four types of configurations.

Further, for a hydrophilic member characterized in that a hydrophilic material is applied to the surface of a substrate, the configuration of the substrate and the first coating and the second coating is one, and The coating and the second coating, the configuration of the third coating is one, the first coating and the second coating are present on both sides of the substrate one each, the first coating and the second coating on both sides of the substrate There are four types of configurations in which the coating and the third coating are present one by one. And
Each hydrophilic material or hydrophilic member has a configuration in which an inorganic binder may be further added to the first coating or the third coating. Of the coatings thus obtained, the first coating is an anti-fogging coating having a moisture absorbing property, and the second coating is an anti-fogging coating with a drip performance.

Here, among the above-mentioned constitutions, as a method for producing a hydrophilic material or a hydrophilic member having no third coating, the first coating is formed on the surface of a base material using the first coating agent. After the step, before applying the second coating agent, curing the first coating agent to form a first coating, and applying the second coating agent thereon, and thereafter curing It is characterized by having. At this time, since the hydrophilic material does not require a base material, an operation of removing the hydrophilic material from the coating film is required. According to the present invention, it is possible to manufacture a hydrophilic material or a hydrophilic member having the above-described droplet function.
Further, the hydrophilic material obtained by this method became a two-layer coating film of the lower layer of the first coating and the upper layer of the second coating, and most of them were clearly identified at the interface between the upper layer and the lower layer. It becomes a hydrophilic material or a hydrophilic member having a two-layer coating film.

Here, among the above-mentioned constitutions, as a method for producing a hydrophilic material or a hydrophilic member in which the third coating is present, the first coating is applied to the surface of the base material without curing the first coating agent. And a method for producing a hydrophilic material or a hydrophilic member, comprising a step of applying the second coating agent thereon before curing, and then curing the second coating agent. . In the present invention, a step of forming a first coating on the surface of a substrate without curing the first coating agent, and a step of applying the second coating agent thereon before being cured, and thereafter curing the second coating agent. By performing the method for producing a hydrophilic material or a hydrophilic member, comprising the above, there is a feature that a hydrophilic material or a hydrophilic member having a drip function as described above can be produced. . When the step of curing the first coating agent as described above is not performed, each component of the second coating agent enters into the first coating agent, and the interface between the upper layer and the lower layer is clearly defined. It becomes a hydrophilic material or a hydrophilic member having an intermediate layer or a three-layer coat film in which a third film exists, which cannot be determined.

The water-absorbing organic polymer used in the present invention mainly refers to an organic polymer having a functional group such as a hydroxyl group, exhibiting an affinity for water and absorbing water. As examples of the water-absorbing organic polymer, polyvinyl alcohol, PVA, polyacrylic acids or polyalkylene oxide, polyvinylpyrrolidone or a polymer thereof can be suitably used. Here, polyvinyl alcohol means a polymer having a vinyl alcohol unit of 70 mol% or more, and has a saponification degree of 70%.
% Or more. The polyvinyl alcohol generally has an average degree of polymerization of 50 to 1,500,000, preferably 80 to 20,000, and more preferably 100 to 20,000.
2,000 and a saponification degree of 60 to 100%, preferably 90 to 100%, more preferably 98 to 100%. In addition, P used in the present invention
VA is obtained by polymerizing a vinyl ester monomer by a known method and saponifying it. The PVA used is not particularly limited. Other suitably used polymers can be obtained by saponifying a copolymer of a vinyl ester monomer and a hydrophilic monomer and / or a hydrophobic monomer in addition to a combination of a vinyl alcohol unit and a vinyl acetate monomer. And vinyl ester monomers such as vinyl formate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, Polymers in combination with vinyl versatate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl oleate, etc., are preferred, with vinyl acetate being economically preferred. These may be used alone or in combination of two or more. Other monomers include hydrophobic monomers such as ethylene, propylene, 1-butene, isobutene, pentene, hexene, octene, 1-dodecene,
Α-olefins such as octadecene, vinyl ethers such as lauryl vinyl ether and vinyl stearate, vinyl 1,1,3,3-tetramethylbutyrate, vinyl 2,2,4,4-tetramethylvalerate, versatic Vinyl esters, higher fatty acid vinyl esters such as other saturated fatty acid vinyl esters,
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate,
Examples include (meth) acrylates such as 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, and octadecyl (meth) acrylate. These may be used alone or in combination of two or more. Further, as hydrophilic monomers, crotonic acid, (meth) acrylic acid, (anhydride) maleic acid, (anhydride) itaconic acid,
3-acrylamide-3,3-dimethylpropyl-trimethyl-ammonium chloride, 3- (meth) acrylamidopropyl-trimethyl-ammonium chloride,
Acrylamide-2-methylpropylsulfonic acid, vinylsulfonic acid, allylsulfonic acid and salts thereof are also included. Further, polyvinyl acetal, polyvinyl butyral, and the like, which are previously cross-linked with an aldehyde compound such as formaldehyde or acetaldehyde, can also be used as a kind of PVA.

The polyacrylic acid is at least one selected from polyacrylic acid, polymethacrylic acid, and salts thereof. Examples of the polyalkylenoxide include polyethylene oxide, polypropylene glycol, and polypropylene oxide, and polyethylene oxide is particularly preferable. Usually, a weight average molecular weight of 30,000 to 1,500,00
0, preferably 500,000 to 750,000 polyalkylene oxides are used.

Other water-absorbing organic polymers include poly-2-hydroxyethyl methacrylate, polyvinylpyrrolidone, polyoxazoline, ethylene vinyl alcohol copolymer, isobutylene maleic anhydride copolymer, polyacrylamide, and polyoxyethylene. Systems, polysaccharides and the like can be suitably used. As the polysaccharide, for the cellulosic, viscose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose,
Hydroxypropyl cellulose, carboxymethyl cellulose and the like can be mentioned. Further, as the polysaccharide,
In the starch system, soluble starch, carboxymethyl starch, dialdehyde starch and the like can be mentioned.

In addition to the water-absorbing organic polymer, 2
Hydroxyethyl methacrylate monomers, sepiolite, silica gel, dextran, alginic acid, sodium alginate, carrageenan, agarose, kaolin and the like can also be used.

The solvent (hereinafter referred to as the first solvent) in the first coating agent used in the present invention is water or toluene, which is generally referred to as an organic solvent,
An aromatic solvent such as xylene or an aliphatic solvent such as glycerin is used. In particular, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-
Organic solvents that are compatible with water, such as propyl alcohol, butyl alcohol, n-butyl alcohol, isobutyl alcohol, ethylene glycol, and xylene, are preferred. This organic solvent is often used with water. The amount of the first solvent is preferably 10 to 10 parts by weight of the water-absorbing organic polymer, or 10 to 10 parts by weight of the inorganic binder such as a zirconium compound, and the total of 100 parts by weight of the water-absorbing organic polymer and the catalyst. 500
00 parts by weight, preferably 100 to 5000 parts by weight, more preferably about 1000 parts by weight.

In the present invention, the first coating
Inorganic fillers in the first coating or third coating
The inorganic filler used in the present invention may contain an
Indah is, for example, one of the materials
(B) a water-absorbing organic polymer such as zirconium acid
For one polyvinyl alcohol, the polymer
Between the hydroxyl group of the binder and the hydroxyl group of the binder.
Response, thereby combining the two materials and
Capable of forming a film with hybrid structure
The resulting coating is hygroscopic and water resistant
This has the effect of forming a coating film having both. The inorganic binder
Examples of Si, Al, Ti, Zr, Ca, Fe,
Selected from the group consisting of V, Sn, Li, Be, B, and P.
Inorganic alkoxides with selected inorganic atoms, zirconium
Including zirconium compounds such as muchelates
Various metal compounds, silica fine particles and the like can be mentioned. this
Among them, a zirconium compound is preferably used. In general
Known zirconium compounds have specific oxidation numbers.
Difficult ZrH_Two, ZrB, ZrC, ZrSi_Two, ZrN,
ZrP, ZrS_Two[Z] having an oxidation number of 0
r ｛P (CH_Three)_Three｝ (Η⁶-toluene)_Two], [Zr
(C₀)_Two(Η ^Two-C_FiveH₆2), ZrCl having an oxidation number of 1, acid
ZrX with chemical number 2_Two(X = Cl, Br, I), oxidation number 3
ZrX_Three(X = F, Cl, Br, I)
Zircon ZrSiO which is a zirconium compound_FourAnd
ZrX which is a zirconium halide_Four(X = F, C
1, Br, I), ZrO_TwoSuch as zirconia, ZrOm
(OH) An oxoacid di of n (m = 4-n, 4 ≧ n ≧ 0)
Ruconium, M4ZrO_Four, M_TwoZrO_Three(M = Na, K,
Zirconates such as 1 / 2Ca, 1 / 2Pb), zirconium nitrate
System, zirconium sulfate, zirconium hydroxide, [ZrF
₆]^2-, [ZrF₈]^Four-Fluoride of zirconium fluoride
Complex, Zr commonly called zirconyl chelate
Zirconium oxychloride of a +2 valence group represented by O
System, zirconium oxychloride, zirconium oxyhydroxide
Conium, zirconium oxynitrate, zirconium oxyacetate
, Zirconium oxysulfate, zirconium oxycarbonate
, Zirconium oxystearate, oxyoctyl
Zirconium luate, and hydrolysis / polycondensation
Zr (OCH_Three)_FourDi like
And ruconium alkoxide. Furthermore, zirconi
Oxide compounds, oxyacid salts, organic acid salts or
Is a complex salt that is aqueous and stable in the processing solution.
Combined with at least one zirconium compound such as zirconyl
It is also possible to use them together. Specifically, ZrO
_Two, ZrO_Two・ XH_TwoO, M_TwoZrO_Three(Zirconic acid and
M) is an alkali metal, ZrO_Three・ 2H_TwoO, K_Four
ZrO_Four・ 2H_TwoO_Two・ 2H_TwoO (periodozirconium
Oxides and related compounds, such as ZrO (H_TwoP
O_Four)_Two, ZrP_TwoO ₇, Oxyacid salts such as ZrSiO4,
Zirconium halides such as roxy zirconium chloride,
Zirconium formate, zirconium acetate, dipropionate
Ruconium, zirconium caprylate, di-stearate
Organic acid zirconium salts such as ruconium, zirconium carbonate
Ammonium, sodium zirconium sulfate, diacetic acid
Ruconium ammonium, zirconium sodium oxalate
, Sodium zirconium citrate, zirconium citrate
Zirconium complex salts such as conium ammonium
It is. These zirconium compounds are
A coating agent that can be added as an inorganic binder to a coating agent
It can be used as a ruconium compound.

The zirconium compound used in the present invention contains at least one of zirconyl chelate and zirconia in the zirconium compound, and may contain two or more kinds of the zirconium compounds. Among them, those containing zirconium oxynitrate or zirconium oxynitrate and zirconia derived from zirconium oxynitrate are preferably used.

In the zirconyl chelate, for example, zirconium chloride, which is one of zirconium halides, is oxidized and changed to zirconyl of zirconium oxychloride. Then, the zirconium oxychloride is further hydrolyzed by the addition of water, and the chloride ion of zirconium oxychloride is replaced by a hydroxide ion to form a chelate complex which is an aggregate containing water ions and chlorine ions. This change also occurs for zirconium nitrate, zirconium sulfate, and the like. Then, deprotonation of the hydroxide ion occurs, and as a result, the hydrolyzate starts polycondensation to form a polymer such as zirconia. At the same time, for example, the OH of a water-absorbing organic polymer such as polyvinyl alcohol present in the first coating agent
The group reacts with the hydrolyzed zirconium compound or the polymer having an OH group to form a composite polymer having an inorganic portion of Zr and an organic portion derived from a water-absorbing organic polymer. When the respective components of the composition are mixed, the hydrolysis reaction and the polycondensation reaction partially proceed as described above. A colloidal sol is obtained by mixing a polymer, a water-absorbing organic polymer, and a polycondensation or cross-linking reaction product of the hydrolyzate derived from the zirconium compound and the water-absorbing organic polymer. This is the first coating agent. At this time, an inorganic compound such as titania or silica or an organic compound such as a surfactant may be mixed as other compounds.

The zirconium nitrate is selected from the group consisting of Zr (NO ₃ )
_In dry air, nitric acid is first released and zirconium oxynitrate ZrO (NO ₃ ) ₂
Changes to Therefore, ordinary commercial products exist in this state. By the way, this reagent, like other zirconyl chelates such as zirconium oxychloride, crosslinks with the water-absorbing organic polymer to form a composite polymer having an inorganic portion of Zr and an organic portion derived from the water-absorbing organic polymer. Can do things. However, when the first coating agent is applied to a substrate to form a film, unlike zirconium oxychloride, there is a disadvantage that the film turns yellow-brown depending on the heating method. On the other hand, like zirconium oxychloride, there are few problems such as corrosion of metal products such as stainless steel piping, and it can cause problems such as damage to the machine even during mass production such as storage and painting with automated machines. There are few advantages.
Zirconium oxysulfate ZrOSO _{4 is} also a relatively easy-to-handle material that does not cause corrosion problems due to contact with metal products, but has a surface where the discoloration of the coating is more likely to occur than with zirconium oxynitrate. From such a comprehensive point of view, it can be understood that zirconium oxynitrate is a preferable material that is easy to handle and is preferable when forming a film having the most moisture absorption, water resistance and transparency among the zirconium compounds.

The biggest problem of the zirconium oxynitrate, that is, the problem of discoloration of the coating to yellow brown, is that nitric acid obtained from nitrate ions present in zirconium oxynitrate and sodium acetate in PVA serve as a catalyst. Thus, it is considered that the cause is oxidation of the OH group of polyvinyl alcohol. Therefore, it is first necessary to remove the nitric acid or nitrate ions in order to prevent discoloration.

The discoloration of the film referred to herein is caused by a heating and drying process after the first coating agent is applied to the base material. It tends to vary depending on the heating temperature and heating time. For example, when a film having a film thickness of 8 μm is to be formed from a composition having a certain composition, 150 μm is required.
Even if the coating is discolored when heated in an atmosphere of ° C. for 20 minutes, discoloration may not occur when heated under conditions less than 1 minute. However, the latter film is a film in an uncured state, and tends to have low water resistance and scratch resistance in many cases. Thus, when the coating is completely cured, the water resistance and scratch resistance are good, but discoloration is likely to occur, and conversely, if it is uncured, it does not discolor, but the water resistance and scratch resistance are reduced, resulting in a vicious cycle . Therefore, if it is possible to find the optimal heating and drying conditions that do not cause discoloration in a state where the coating is completely cured, a coating without discoloration can be obtained.
Therefore, the problem of discoloration of the film can be solved by minimizing the content of nitrate ions in the first coating agent and finding out the optimal conditions of heating and drying.

There are various methods for minimizing the nitrate ion. The most efficient method is to remove the nitrate ion from the zirconium oxynitrate solution using an anion exchange resin. Thus, the more nitrate ions are removed, the less discoloration of the coating produced thereby. However, conversely, the viscosity of the first coating agent or the third coating agent from which the film is formed increases sharply, and if it is excessively applied, it changes into an agar-like solid. Therefore, the amount to be removed is limited. The removal amount of this nitrate ion is controlled by the pH of the aqueous solution of zirconium oxynitrate. In the case of an aqueous solution of zirconium oxynitrate having a solid content of 8 to 10%, the pH is controlled to be in the range of 1.5 to 4. ,
Removal of nitrate ions by anion exchange resin is preferred,
More preferably, the pH is 2.5 to 3. When the pH value is lower than the above, the discoloration of the coating is remarkable. Thus, in order to reduce the discoloration of the film and to prepare the coating solution without causing an extreme increase in the viscosity of the solution in the coating solution of the coating agent, the coating solution must have a pH of 1.5 or more.
When the zirconium compound is used, the amount of the zirconium compound to be used is preferably 10 to 200 parts by weight, more preferably 50 to 150 parts by weight, based on 100 parts by weight of the total of the water-absorbing organic polymer and the catalyst. Conversely, when the coating solution has a pH of 1.5 or less, the amount of the zirconium compound used is preferably 1 to 10 parts by weight based on 100 parts by weight of the total of the water-absorbing organic polymer and the catalyst. More preferably, it is 2 to 5 parts by weight.

The anion exchange resin used at this time is not particularly limited as long as it can exchange anions such as nitrate ions. As the functional group of the ion exchange resin, an amine type such as dimethylethanolamine and trimethylamine, and a quaternary ammonium type can be used. The shape of the obtained zirconia may be any of a granular shape and a chain shape, and is not particularly limited.

In the present invention, as a method for reducing the discoloration of the coating, the degree of saponification of the polyvinyl alcohol (or PVA) is preferably set to 95% or more, and more preferably 98%. % Or more. Such a method, as the inorganic binder,
This is noticeable when zirconium oxynitrate is used.
As a cause of such discoloration, sodium acetate contained in PVA acts as an accelerator, decomposition of PVA starts, and P
It is considered that VA is discolored from yellow to tan. Therefore, PVA having a high degree of saponification has fewer vinyl acetate groups in accordance with the degree of saponification, and the amount of sodium acetate obtained by liberating the vinyl acetate also naturally decreases. Since the amount of sodium acetate as the agent is small, it is considered that the decomposition of PVA is suppressed and the discoloration of the film is suppressed accordingly.

Further, as described above, as the inorganic binder, at least one of an inorganic alkoxide and the alkoxide, or a polymer having an OH group formed by hydrolysis and polycondensation thereof is used. Is also good. The inorganic alkoxide used in the invention is, for example, at least one compound represented by the following formula (1). M (OR) _n (X) _an (1) where M is Si, Al, Ti, Zr, Ca, Fe,
V is an inorganic atom selected from the group consisting of Sn, Li, Be, B, and P; R is an alkyl group;
Is an alkyl group, an alkyl group having a functional group, or a halogen, a is a valence of M, and n is 1
To a. Among the compounds of the formula (1), n
= A, that is, a compound in which only an alkoxy group is bonded to M is widely used.

When M is Si, the alkoxide is
It is represented by Si (OR1) ₄ . Here, R1 is preferably a lower alkyl group having 1 to 4 carbon atoms. Such alkoxysilanes include Si (OCH ₃ ) ₄ , Si (OC
₂ H ₅ ) _{4 and the} like. When M is Al, the alkoxide is represented by Al (OR2) ₃ . Where R2
Is preferably a lower alkyl group. Such aluminum alkoxides include Al (OCH ₃ ) ₄ , A
l (OC ₂ H ₅ ) ₃ , Al (On-C ₃ H ₇ ) ₃ , Al
_{(O-iso-C 3 H} 7) 3, such as Al (OC ₄ H _{9) 3} and the like. The aluminum alkoxide may be used as a mixture of two or more kinds. Such an aluminum alkoxide is usually used in a mixture with the alkoxysilane, and the use of the aluminum alkoxide improves the light transmittance and heat resistance of the obtained film. The amount of the aluminum alkoxide to be used is preferably in the range of 10 parts by weight or less, more preferably about 5 parts by weight, based on 100 parts by weight of the alkoxysilane. If the amount exceeds 10 parts by weight, the formed polymer tends to gel, and the resulting coating film may be cracked. When the M is Ti, the alkoxide is Ti
(OR3) It is represented by ₄ . Here, R3 is preferably a lower alkyl group. Such titanium _{alkoxide, Ti (O-CH 3)} 4, Ti (O-C
_{2 H 5) 4, Ti (} O-n-C 3 H 7) 4, Ti (O-iso-
_{C 3 H 7) 4, Ti} (O-C 4 H 9) 4 and the like.
The titanium alkoxides may be used as a mixture of two or more kinds. Such a titanium alkoxide is usually used in a mixture with the alkoxysilane, and by using the titanium alkoxide, the UV resistance of the obtained coating is improved and the heat resistance of the coating is also significantly improved. The amount of the titanium alkoxide used is within a range of 3 parts by weight or less, preferably about 1 part by weight, based on 100 parts by weight of the alkoxysilane. If the amount exceeds 3 parts by weight, the formed polymer becomes brittle, and the coating tends to peel off when the substrate is coated.

When M is Zr, the alkoxide is represented by Zr (OR ₄ ) ₄ . Here, R4 is preferably a lower alkyl group. Such zirconium alkoxides include Zr (OCH ₃ ) ₄ and Zr (OC _{2
H 5) 4, Zr (O} -iso-C 3 H 7) 4, Zr (O-t-C
_{4 H 9) 4, Zr (} O-n-C 4 H 9) 4 and the like.
The zirconium alkoxides may be used as a mixture of two or more kinds. Such a zirconium alkoxide is usually used as a mixture with the alkoxysilane,
By using the zirconium alkoxide, the toughness and heat resistance of the obtained film are improved. The amount of the zirconium alkoxide used is within a range of 5 parts by weight or less, preferably about 3 parts by weight, based on 100 parts by weight of the alkoxysilane.
Parts by weight. If it exceeds 5 parts by weight, the formed polymer tends to gel, the brittleness of the polymer increases, and the coating tends to peel off when the substrate is coated.

Other alkoxides include, for example, Ca (OC ₃ H ₅ ) ₂ , Fe (OC ₂ H ₅ ) ₃ , V (O-
iso-C ₃ H ₇ ) ₄ , Sn (Ot-C ₄ H ₉ ) ₄ , Li (O
C ₂ H ₅ ), Be (OC ₃ H ₅ ) ₂ , B (OC ₂ H ₅ ) ₃ , P
(OC ₂ H ₅ ) ₂ and P (OCH ₃ ) ₃ . Among the inorganic alkoxides represented by the formula (1), when n = a-1 or less, that is, as a compound in which a group X other than alkoxy is bonded to M, for example, X is a halogen such as Cl or Br. There are compounds. A compound in which X is a halogen is hydrolyzed in the same manner as an alkoxy group to generate an OH group, and a polycondensation reaction occurs. X may also be an alkyl group or an alkyl group having a functional group, and the alkyl group usually has 1 to 15 carbon atoms. Such groups remain as organic moieties in the resulting polymer without hydrolysis.
As the functional group, a carboxyl group, a carbonyl group,
Examples include an amino group, a vinyl group, and an epoxy group. Compounds of the formula (1) having X include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ
-Aminopropylmethoxysilane and the like. The amount of the inorganic alkoxide to be used is preferably 1 to 100 parts by weight in total of the water-absorbing organic polymer and the catalyst.
20 parts by weight, more preferably 5 to 10 parts by weight. These inorganic binders may be used alone with a zirconium compound or an inorganic alkoxide, or may be used by mixing two or more kinds of other inorganic binders.

The first coating agent, the first coating or the third coating may further contain at least one water-absorbing inorganic composition. Examples of the water-absorbing inorganic composition include sepiolite and silica gel. In the first coating agent, the first coating film or the third coating film used in the present invention, the catalyst includes a hydrolysis catalyst and a curing catalyst. The hydrolysis catalyst,
Used for hydrolysis of zirconium compounds and inorganic alkoxides. Therefore, a zirconium compound or
If an inorganic alkoxide is partially hydrolyzed and polycondensed and a polymer having OH groups (which can be a relatively low molecular weight oligomer) is used, a hydrolysis catalyst may be unnecessary.

The hydrolysis catalyst includes hydrochloric acid, sulfuric acid,
Mineral acids such as nitric acid are used. Anhydrides of mineral acids, such as hydrogen chloride gas, may also be used. In addition, organic acids and their anhydrides can also be used. For example, tartaric acid, phthalic acid, maleic acid, dodecylsuccinic acid, hexahydrophthalic acid, methylnadic acid, pyromellitic acid, benzophenonetetracarboxylic acid, dichlorosuccinic acid, chlorendic acid, phthalic anhydride, maleic anhydride, Examples include dodecylsuccinic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, dichlorosuccinic anhydride, chlorendic anhydride, and the like. Further, inorganic bases such as sodium hydroxide, potassium hydroxide, and ammonia are also used as catalysts. These hydrolysis catalysts are used in an amount of 0.01 to 0.5 part by weight, preferably 0.015 to 0.3 part by weight, based on 100 parts by weight of the inorganic binder. 0.
If the amount is less than 01 parts by weight, the hydrolysis may be insufficient. If the amount exceeds 0.5 parts by weight, the polycondensation reaction may proceed and the viscosity may increase.

The curing catalyst is mainly used as a hydrolyzate of an alkoxide or a polycondensation reaction catalyst of a zirconium compound, and as a catalyst for a cross-linking reaction of a water-absorbing organic polymer. , A zirconium compound and a water-absorbing organic polymer as a catalyst for a polycondensation reaction and / or a crosslinking reaction. Examples of such curing catalysts include 1,8-diazabicyclo [5.4.0] undecene-7, quaternary phosphonium salts, organic amines, amino acids, metal acetylacetonates, metal salts of organic acids, Lewis acids, and peroxides. At least one of an oxo acid such as a substance and a perchloric oxide or an oxo acid salt can be suitably used.

The quaternary phosphonium salts include tetrabis (hydroxymethyl) phosphonium chloride,
Tetrabutylphosphonium bromide and the like.
Examples of the organic amine include ethylamine, dimethylamine, N, N-dimethylamine, tributylamine, tri-n-propylamine, tripentylamine, tripropargylamine, N, N, N-trimethylethylenediamine, n-hexylamine and the like. Is mentioned.

The amino acids include glycine and the like. Examples of the metal acetylacetonate include aluminum acetylacetonate, indium acetylacetonate, chromium acetylacetonate, titanium acetylacetonate, and cobalt acetylacetonate. In the metal acetylacetonate, preferably, aluminum acetylacetonate is used.

Examples of the organic acid metal salts include sodium acetate, zinc naphthenate, cobalt naphthenate, zinc octylate, tin octylate and the like.

Examples of the Lewis acid include stannic chloride, aluminum chloride, ferric chloride, titanium chloride, zinc chloride, antimony chloride and the like.

The peroxide includes hydrogen peroxide.

Examples of the above-mentioned perchloric oxide include lithium perchlorate. The oxo acids and salts thereof include, in addition to the peroxides and perchloric oxides, orthoboric acid, metaboric acid, trimetaboric acid, hypoboric acid, carbonic acid, cyanic acid, isocyanic acid, thunderic acid, orthosilicic acid , Metasilicic acid, peroxonitrate, nitrous acid, peroxonitrite, nitroxylic acid, hyponitrite, phosphoric acid, diphosphoric acid, pyrophosphoric acid, triphosphoric acid, polyphosphoric acid, polyphosphoric acid, metaphosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid Phosphoric acid, peroxophosphoric acid, peroxoniric acid, hypophosphoric acid, diphosphoric acid, phosphite, diphosphorous acid, hypophosphorous acid, arsenic acid, arsenous acid, hexahydroantimonic acid,
Disulfuric acid, peroxosulfuric acid, peroxoniline sulfuric acid, thiosulfuric acid, dithiosulfuric acid, sulfurous acid, bisulfite, thiosulfite, nitrous acid, sulfoxylic acid, polythionic acid, selenic acid, selenous acid, telluric acid, chromic acid, dichromic acid, Chloric acid, chlorite, hypochlorous acid, bromate, bromate, hypobromite, periodate, iodate, hypoiodite, permanganate, manganate, pertechnetate, technetate, Examples thereof include perrhenic acid, rhenic acid and the like, and salts thereof.

The amount of the curing catalyst used is preferably the total of the inorganic binder such as a zirconium compound, an alkoxide and a polymer having an OH group, and the water-absorbing organic polymer in the first coating agent or the third coating agent. 0.01 to 100 parts by weight
It is 2 parts by weight, more preferably 0.05 part by weight.
If the amount is more than 2 parts by weight, the polycondensation proceeds rapidly, so that it is difficult to dissolve in the organic solvent, and the resulting coating becomes non-uniform, so that the strength may be reduced.

Further, the first coating agent, the first coating or the third coating may further contain at least one kind of polyacrylic acid. As the polyacrylic acids, polyacrylic acid, polymethacrylic acid,
These salts are exemplified. The amount of the polyacrylic acid used is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the solid content in the first coating agent, the first coating or the third coating. When the amount is less than 0.1 part by weight, the obtained composition may have a low water absorption speed, and when it exceeds 10 parts by weight, the obtained composition may be tacky. In particular, when the obtained composition is applied to a member having hardness, the polyacrylic acid is used in an amount of 0.1 to 0.
Preferably, it is used in a proportion in the range of 5 parts by weight. 0.
If the amount exceeds 5 parts by weight, the hardness of the film formed by the obtained coating agent may be low.

In the present invention, the first coating agent, the first coating or the third coating may further contain a fluorine-containing surfactant containing a hydrophilic group. Examples of the fluorinated surfactant to be contained include perfluoroalkyl carboxylate, perfluoroalkyl ammonium salt, perfluoroalkyl betaine, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl group-containing oligomer, trifluoropropyl trichlorosilane, Trifluoropropylbromosilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, heptadecafluorooctyltrimethoxysilane, heptadecafluorooctyltriethoxysilane, and the like can be suitably used.

In the present invention, the first coating agent, the first film or the third film may further comprise:
A heat ray absorbing material may be included, and if it is used for a transparent material such as glass, it is possible to suppress an increase in the indoor temperature due to radiation such as sunlight and raise the temperature of the glass surface to make it difficult for water droplets to adhere. it can.

Silver ions can be suitably used as the heat ray absorbing material. In the present invention, the first coating agent, the first coating, or the third coating may further contain a heat storage material, accumulate radiant heat such as sunlight, and increase the temperature of the glass surface. Can be kept high to make it difficult for water droplets to adhere. As the heat storage material, high-density polyethylene, paraffin, or the like can be suitably used.

In the present invention, an ultraviolet absorber may be contained in the first coating agent, the first coating, or the third coating, and if it is used for a transparent material such as glass, it can be applied to the human body. It can block harmful short wavelength sunlight.

Examples of the ultraviolet absorber include benzotriazole-based, benzophenone-based, salicylate-based, cyanoacrylate-based, oxanilide-based, and Ce. In the present invention, an antimicrobial agent may be contained in the first coating agent, the first coating film, or the third coating film, so that the generation and propagation of mold and bacteria can be prevented.
Antibacterial agents include sodium sulfonate, isothiazoline, benzoic acid, 10,10-oxybisphenoxyarsine, 2- (4-thiazolyl) -benzimidazole, N- (fluorodichloromethylthio) -phthalimide, 2-methylcarbo Neilaminobenzimidazole, silver, copper, zeolite, silver zirconium phosphate, silver hydroapatite, silver phosphate glass, silver phosphate ceramic, and the like.

The hydroxyl group-containing organic compound used in the present invention is a material that is water-soluble and acidic, and is an industrially preferable material from the viewpoint of safety and ease of management. Specific examples thereof include benzoic acid, monocarboxylic acids such as stearic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, fumaric acid, maleic acid, phthalic acid, lactic acid, tartaric acid, citric acid, Examples thereof include carboxylic acid-containing low molecules such as malic acid and carboxylic acid-containing polymers such as polyacrylic acid. Among these carboxylic acid-containing compounds, succinic acid, tartaric acid and citric acid are even more preferably used. Any carboxylic acid-containing compound may be used in the composition of the present invention, depending on the method of use, and these components are not limited to one type, and two or more types may be blended.

In the present invention, by adding the hydroxyl group-containing organic compound to the first coating agent, the first coating or the third coating, the dropping performance of the obtained coating and the upper layer And the lower layer or the upper layer, the intermediate layer and the lower layer. The amount of the hydroxyl-containing organic compound is 10 parts by weight or less, preferably 0.001 to 10 parts by weight, based on 100 parts by weight of the water-absorbing organic polymer, the inorganic binder, and the catalyst.
It is more preferably 0.01 to 5 parts by weight, and still more preferably 0.1 to 4 parts by weight. The appropriate addition amount of the carboxylic acid-containing compound of the present invention is determined by the amount of the inorganic binder, and when the amount of the inorganic binder is large, it may aggregate depending on the amount of the carboxylic acid-containing compound added. .

An aldehyde compound such as formaldehyde may be added as a cross-linking agent to the first coating agent, the first coating or the third coating, and by adding them, polyvinyl alcohol is added to formaldehyde. And has the advantage that a film having good water resistance and being hardly attacked by strong alkali chemicals can be obtained. In addition to the formalization with an aldehyde compound such as acetaldehyde, there is also a merit that the chemical resistance of the coating is improved by benzalization or butyralization. Examples of the aldehyde compound include a dialdehyde compound and a monoaldehyde compound. , Heptanedial, octanedial, nonandial, decandial, dodecandial, 2,4-dimethylhexanedial, 5-methylheptanedial, 4-methyloctanedial,
Compounds such as 2,5-dimethyloctanedial and 3,6-dimethyldecandial, or aromatic compounds such as orthophthalaldehyde, isophthalaldehyde, terephthalaldehyde, and phenylmalondialdehyde;
Alternatively, an alicyclic compound such as 1,4-cyclohexanedialdehyde can be used. Alternatively, compounds obtained by reacting these dialdehyde compounds with alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, and propylene glycol to acetalize both terminals or one terminal of the dialdehyde compounds are mentioned. These compounds may be used alone or as a mixture of two or more. However, malondialdehyde, succinaldehyde, glutaraldehyde, hexanedial, heptanedial, Octanedials, nonandials, or their acetalized compounds are preferred. Examples of the monoaldehyde compound include known compounds such as formaldehyde and benzaldehyde, and formaldehyde is preferred from the viewpoint of minimizing a decrease in the strength of a film formed by the composition. Although the degree of acetalization by these aldehyde compounds is not particularly limited, the carboxylic acid-containing compound and the water-absorbing organic polymer, or the water-absorbing organic polymer, the inorganic binder, the catalyst, and the like, are preferably 1 to 50 parts by weight. Parts by weight, preferably 10 to 30 parts by weight. More preferably, it is 15 to 20 parts by weight.
If the amount is less than 1 part by weight, the moisture and heat resistance is not sufficient.

A surfactant may be added to the first coating agent, the first coating or the third coating,
By adding them, there is an advantage in that the coating agent or the coating film obtained thereby can improve the dropping performance. Examples of the surfactant include polyoxyethylene alkylphenyl ether ammonium sulphonate, sodium polyoxyethylene alkylphenyl ether sulphonate, fatty acid sodium soap, fatty acid soap, dioctisulfosuccinate sodium, and alkyl sulphate. , Alkyl ether sulfate, alkyl sulfate soda salt, alkyl ether sulfate soda salt, alkyl sulfate TEA
Salt, polyoxyethylene alkyl ether tersulfate soda salt, polyoxyethylene alkyl ether tersulfate, polyoxyethylene alkyl ether tersulfate TEA salt, sodium 2-ethylhexylalkyl sulfate, sodium acylmethyltaurate Sodium lauroylmethyltaurate, sodium dodecylbenzenesulfonate, disodium lauryl sulfosuccinate, disodium lauryl polyoxyethylenesulfosuccinate, polycarboxylic acid, oleoyl sarcosine, amide ether sulphate, lauroyl sarcosine, Anionic surfactants such as sulfo FA ester sodium salt; polyoxyethylene lauryl ether;
Polyoxyethylene tridecyl ether, polyoxyethylene steatyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkylphenyl ether, polyoxy Ethylene laurate, polyoxyethylene stearate, polyoxyethylene oleate, sorbitan stearate, sorbitan alkyl ester, polyoxyethylene sorbitan alkyl ester, polyether-modified silicone, polyester-modified silicone Sorbitan laurate, sorbitan palmitate, sorbitan oleate, sorbitan sesquioleate, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan stearate,
Polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan oleate, glycerol stearate, polyglycerin fatty acid ester, alkyl alkyl amide, lauric acid ethanolamide, oleic acid ethanolamide, polyoxyethylene Nonionic surfactants such as alkylamine, polyoxyethylene stearate, and polyoxyethylene alkylpropylenediamine; alkyldimethylbenzylammonium chloride, 1-hydroxyethyl2-alkylimidazoline quaternary salt, alkylisoquinolinium bromide, Polymeric amine, alkyltrimethylammonium chloride, alkylimidazoline quaternary salt, dialkyldimethylammonium chloride, octadecylamine acetate,
Cationic surfactants such as alkyl propylene diamine acetate, tetradecylamine acetate, dioleyl dimethyl benzyl ammonium chloride and the like; amphoteric surfactants such as dimethyl alkyl betaine, alkyl glycine, amido betaine and imidazoline can be suitably used.

In the present invention, fine zirconia particles may be dispersed in the first coating agent, the first coating film, or the third coating film. The range of 1 nm to 300 nm is preferred. More preferably, 0.5 nm to 4 nm
Is preferable. When the average particle diameter is lower than 0.1 nm, the appearance during film formation is deteriorated, and when, for example, zirconium nitrate or the like is used, coloring becomes easy. Also, 300n
Zirconia having an average particle diameter of more than m causes deterioration of the transparency of the formed coating film. The first coating agent, the first coating, or the fine zirconia in the third coating is derived from zirconyl such as zirconium nitrate. , Its particle size can be increased. But,
If the pH is set as neutral as possible with an anion exchange resin or the like before heating, heating can increase the particle size more quickly. For example, in a 20% by weight aqueous solution of zirconium nitrate, the reaction from zirconium nitrate to zirconia hardly proceeds due to excess nitrate ions and hydrogen ions as it is, and the particle size hardly grows.
Further, even if it grows, a coating agent using the same can only form a film having a problem in cleaning properties and the like. However, if nitrate ions are removed in advance with an anion exchange resin, the reaction proceeds promptly and the particle size grows, and a coating agent using this can form a coating having no problem in terms of cleanability and the like. And the optimal pH is
Although it depends on the solid content, pH 1.5 to pH 3 is preferable,
More preferably, the pH is 2 to 2.5. This pH adjustment also has the effect of removing the disadvantage of the coating becoming dark brown when using zirconium nitrate. However, if the pH is too high, the viscosity of the coating agent becomes high, making it difficult to handle. Also, if the anion exchange resin used at this time ion exchanges anions such as nitrate ions,
There is no particular limitation. As the functional group of the ion exchange resin, an amine type such as dimethylethanolamine and trimethylamine, and a quaternary ammonium type can be used. The shape of the obtained zirconia may be any of a granular shape and a chain shape, and is not particularly limited. Further, in the present invention, in the first coating agent, the first coating, or the third set coating, in addition to titania, silica, alumina, and zirconia which are fine-particle inorganic oxides, yttrium oxide, niobium oxide, An oxide such as cerium oxide may be added.

The first metal ion used in the present invention may be any ion as long as it is a metal ion, such as Ag, Cu, Zn, Y, Fe, which forms a metal cation (Mn +).
In addition to transition metals such as Ni, Ti, Zr, and Cr, Li, Na,
Alkali metals such as K, Rb, Cs and Fr; alkaline earth metals such as Ca, Sr, Ba and Ra; typical metal elements such as Al, Mg, Ga and Sn; and rare earth metals such as La, Nd and Gd Can be mentioned. Among these, L which forms monovalent cations
Alkali metal ions such as i, Na, K, Rb, Cs, and Fr are preferable, and among monovalent cations, alkali metal ions such as K, Rb, Cs, and Fr are larger in size than other ions. Is more preferred because The amount of addition is 0.1 parts by weight or more, preferably 0.1 part by weight, based on 100 parts by weight of the water-absorbing organic polymer, the inorganic binder, and the catalyst, which are solids in the first coating agent. 1 to
It is 10 parts by weight, more preferably 1 to 5 parts by weight, even more preferably 1.5 to 4 parts by weight.

The second coating agent used in the present invention,
As the hydrophilic inorganic oxide in the second coating or the third coating, silica (SiO2), alumina (Al2O3),
It is composed of a single component inorganic oxide colloid or inorganic oxide fine particles selected from the group consisting of zirconia (ZrO2), titania (TiO2), ceria (CeO2), and SnO2, a mixture thereof, and two or more of these components. Composite inorganic oxide fine particles are used. These are preferably used in the form of a sol.

Further, as the hydrophilic inorganic oxide in the second coating agent, the second coating or the third coating used in the present invention, the inorganic alkoxide and the alkoxide or the alkoxide obtained by hydrolysis and polycondensation thereof may be used. O formed
A polymer having an H group is also preferably used. These polymers may be used together with the composite inorganic oxide fine particles, or two or more of them may be mixed and used. Further, the zirconium compound which has been converted into an oxide by a reaction method such as heating, pressurizing, adjusting pH, adding a catalyst and the like may be used as the hydrophilic inorganic oxide.

Examples of the inorganic oxide fine particles include, for example, "Snowtex-OL", "Snowtex-O", "Snowtex-OUP", "Snowtex-UP", "Snowtex-UP", which are silica sols manufactured by Nissan Chemical Industries, Ltd. A sol solution having an acidic pH such as "Snowtex-AK" is preferably used. The dispersion medium of the sol is an organic solvent or an alcohol, such as “Snowtex-MA-ST-M”, “Snowtex-IPA-”.
ST, Snowtex-EG-ST, Snowtex-EG-ST-ZL, Snowtex-NP
A sol solution such as "C-ST" can also be used. Also, the company's alumina sol “Alumina sol 520”, its company's zirconia sol “NZS-30A”, the colloidal silica “PL-1”, “PL-2” and “PL-3” of Fuso Chemical Co., and the alumina sol of Kawaken Fine Chemical Co., Ltd. “Aluminum sol 10”, “alumina clear sol”, titania sol “CS-N”, “STS-01”, “STS-02”, manufactured by Ishihara Sangyo Co., Ltd.
Ceriasol “Needral U-1” manufactured by Taki Kagaku Co., Ltd.
5 ", titania sol" M-6 "and other commercially available aqueous dispersion sols," ST-K01 "and" ST-K "manufactured by Ishihara Sangyo Co., Ltd.
03 ", a commercially available water-alcohol mixed solvent-dispersed titania sol containing a binder, and the like.

The size of the inorganic oxide fine particles is as follows.
~ 300 nm is preferred. When the particle size is less than 4 nm, the arithmetic average roughness (Ra) tends to be less than 1.5 nm, and the average interval (Sm) of the unevenness tends to be less than 4 nm. Therefore, it is not possible to form an uneven shape effective for improving the droplet performance and the droplet persistence, which is not preferable. The particle size is 300 nm
When the average roughness (Ra) exceeds 80 nm, and the average interval (Sm) of the irregularities exceeds 300 nm, the irregularities are too large. Therefore, it is not preferable because transparency is lost and fine particles are liable to settle in a manufacturing process.

The finely divided hydrophilic inorganic oxide to be mixed in the second coating agent, the second coating or the third set coating has an average particle diameter in the range of 4 nm to 300 nm as described above. Is preferable, and 40 nm to
It preferably has an average particle size in the range of 100 nm.
In addition, the shape of the chain is preferably a chain shape rather than a granular shape because the shape is better in terms of the dropping performance. As an example of the silica which is the finely divided hydrophilic inorganic oxide, silica sol can be mentioned. It is a colloidal dispersion of high molecular weight silicic anhydride in an organic solvent such as water and / or alcohol. In the present invention, the average particle size is 4 to 200 nm.
When the average particle size is less than 5 nm, the stability of the dispersed state is poor, and when the average particle size exceeds 300 nm, the transparency of the resulting coating film is poor.

Here, the Ra value and the Sm value are based on JIS B 0
601 (1994) and an atomic force microscope (for example, SPI37 manufactured by Seiko Denshi Co., Ltd.)
00) and an electron microscope (for example, H
-600) can be calculated from the cross-sectional curve observed and measured.

The hydrophilic inorganic oxide fine particles may be silica alone, but more preferably a mixture of silica and alumina. In the case of using only alumina, there is a surface where adhesion to the lower layer is weaker than that of silica. However, it has a characteristic that it has higher resistance to high temperature and humidity than silica.
In addition, silica has a surface with higher adhesiveness to the lower layer than alumina, but has a feature in that high-temperature and high-humidity resistance is inferior to alumina. Therefore, if this alumina and silica are mixed at a certain mixing ratio, each of them has a surface capable of compensating for a defect due to its advantages. In order to form a layer coat, these mixtures are considered to be preferable. And. The mixing ratio is preferably such that the weight of alumina is from 10 to 1000 parts by weight, more preferably from 50 to 200 parts by weight of alumina, and even more preferably from 70 to 150 parts by weight of alumina based on 100 parts by weight of silica. Parts by weight.

The hydrophilic inorganic oxide fine particles are preferably chain fine particles. By using the chain-shaped fine particles, the shape of the surface unevenness becomes a three-dimensionally intricately uneven shape, so that it is possible to form a surface unevenness with high droplet performance and long lasting droplet. Examples of chain colloids include "Snowtex-OUP" and "Snowtex-UP", which are silica sols manufactured by Nissan Chemical Industries, Ltd.

The solvent for dispersing the hydrophilic inorganic oxide fine particles is not particularly limited as long as the inorganic oxide fine particles are substantially stably dispersed, but is preferably a simple substance or a mixture of water, ethanol, propanol and the like. Water is more preferred.

When the hydrophilic inorganic oxide or the hydrophilic inorganic oxide fine particles are added to the solution containing the carboxylic acid-containing compound, a dispersing aid may be added. The dispersing aid is not particularly limited, and is generally used as a dispersing aid, for example, electrolytes such as sodium phosphate, sodium hexametaphosphate, potassium pyrophosphate, aluminum chloride, iron chloride, various surfactants, and various organic polymers. , A silane coupling agent, a titanium coupling agent and the like. The addition amount is usually 0.01 to 5% by weight based on the inorganic oxide fine particles.

In the present invention, a carboxylic acid-containing compound is used in the second coating agent, the second coating or the third coating, and specific examples thereof include monobenzoic acid and stearic acid. Carboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, fumaric acid, maleic acid, phthalic acid, lactic acid, tartaric acid,
Examples thereof include carboxylic acid-containing low molecules such as citric acid and malic acid, and carboxylic acid-containing polymers such as polyacrylic acid. Among these carboxylic acid-containing compounds, succinic acid, tartaric acid and citric acid are even more preferably used. Any carboxylic acid-containing compound may be used in the composition of the present invention, depending on the method of use, and these components are not limited to one type, and two or more types may be blended. In addition, the compounding amount of the carboxylic acid-containing compound may be a hydrophilic inorganic oxide 100
0.01 to 1000 parts by weight based on parts by weight,
It is more preferably from 10 to 500 parts by weight, even more preferably from 100 to 400 parts by weight.

The solvent (hereinafter referred to as the second solvent) used in the second coating agent used in the present invention is water or other aromatic solvents such as toluene and xylene which are generally called organic solvents. Aliphatic solvents and aliphatic solvents such as glycerin are used. In particular, water-compatible organic solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, and butyl alcohol are preferred. is there. This organic solvent is often used with water. The amount of the second solvent used is preferably 100 to 50 parts by weight of the hydrophilic inorganic oxide and 100 parts by weight of the carboxylic acid-containing compound.
000 parts by weight, more preferably 1000 to 1000 parts by weight.
50,000 parts by weight.

In the present invention, the second coating agent is a coating solution in which the hydrophilic inorganic oxide is mixed with the carboxylic acid-containing compound and dispersed in a water-containing organic solvent in a colloidal state. . In this solution, for example, an OH group in the inorganic oxide such as silica sol undergoes a dehydration condensation reaction with an OH group of a carboxylic acid-containing compound such as tartaric acid, whereby both compounds are bonded via oxygen to form an inorganic compound. A composite polymer having the oxide and the carboxylic acid-containing compound is formed. Then, by coating this solution on the first coating, the OH group of the water-absorbing organic polymer in the first coating and the OH of the carboxylic acid-containing compound
The group and the OH group of the inorganic oxide in the second coating and the OH group of the carboxylic acid-containing compound are bonded by the dehydration condensation reaction as described above, and form a lower layer of the first coating. It is considered that the upper layer comes into close contact with the upper layer of the second coating. In this way, the lower layer which is the first film having moisture absorption performance, the two-layer coating film obtained by coating the upper layer which is the second film having dropping performance, or the first film and the second film. A hydrophilic coating, which is a three-layer coating in which the third coating is present, is obtained. Among the carboxylic acid-containing compounds, citric acid and tartaric acid particularly have a large number of OH groups. By using them, a hydrophilic film having particularly high scratch resistance, high temperature resistance and high humidity resistance can be obtained.

The second metal ion used in the present invention may be any ion as long as it is a metal ion, such as Ag, Cu, Zn, Y, Fe, which forms a metal cation (Mn +).
In addition to transition metals such as Ni, Ti, Zr, and Cr, Li, Na,
Alkali metals such as K, Rb, Cs and Fr; alkaline earth metals such as Ca, Sr, Ba and Ra; typical metal elements such as Al, Mg, Ga and Sn; and rare earth metals such as La, Nd and Gd Can be mentioned. Among them, C which forms a divalent cation
In addition to transition metals such as u, Zn, Fe, and Cr, Ca, Sr, Ba,
Alkaline earth metals such as Ra, typical metal elements such as Mg, Ga and Sn, and rare earth metals such as La, Nd and Gd are preferable. Among divalent cations, metal ions such as Mg and Ca are preferred. Is particularly preferable as compared with the ion of The amount of addition is 0.1 parts by weight based on 100 parts by weight of the hydrophilic inorganic oxide and the carboxylic acid-containing compound as solids in the second coating agent, the second coating, or the third coating. Or more, preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, still more preferably 1.5 to 4 parts by weight.
Parts by weight.

In the present invention, a catalyst may be further added to the second coating agent, the second coating film or the third coating film, and the catalyst may be the one used in the first coating agent. The same hydrolysis catalyst and curing catalyst as described above can be suitably used. And these catalysts, as described above, the second coating agent, the second coating, or the OH group of the hydrophilic inorganic oxide in the third set coating, and the OH group of the carboxylic acid-containing compound and Has the effect of promoting the dehydration-condensation reaction of the compound, thereby strengthening the bond between the two compounds.

In the present invention, an inorganic binder may be further added to the second coating agent, the second film or the third film, and the inorganic binder may be used in the first coating agent. The same zirconium compounds and inorganic alkoxides as described above are preferably used. And these inorganic binders, the second coating agent, the second coating, or the OH group of the inorganic oxide in the third set of coatings, the OH of the carboxylic acid-containing compound has
In addition to causing a dehydration condensation reaction between the base and the group, it serves to strengthen the bond between the inorganic oxides, and lowers the bonding force between the lower layer in the first coating and the upper layer in the second coating. This has the effect of increasing the coating and creating a coating with high scratch resistance.

In the present invention, a surfactant may be further added to the second coating agent, the second coating or the third coating, and the surfactant includes the first coating agent, The same surfactants used in the first or third set of coatings are preferably used. And, by adding these surfactants, the wettability of the upper layer can be improved by adding it, and it is possible to express the drip property without applying water to the film, and to scratch the water on the film. There is an effect that it can be used even in places where operation is difficult.

In the present invention, the water-absorbing organic polymer may be further added to the second coating agent, the second film, or the third group film. The same water-absorbing organic polymer as used for the coating agent is preferably used. By adding these water-absorbing organic polymers, the wettability of the upper layer is improved, and the hydrophilic material obtained thereby improves the drip performance as compared with those without the addition. Has an effect.

According to the present invention, as a method of forming the hydrophilic material, a step of forming the first coating by curing the first coating agent as described above, and a step of forming the first coating on the first coating A method for producing a hydrophilic material, comprising: curing the two coating agents to form a second coating, and forming a first coating without curing the first coating agent, 2) a method for producing a hydrophilic member, comprising a step of applying the second coating agent from above, before curing, and thereafter curing.
There are different ways. The former is a two-layer coating film in which the interface between the upper layer and the lower layer can be clearly identified, and the latter is a three-layer coating film in which the interface cannot be identified. And, for example, the former is formed as follows. First, the components of the first coating agent are mixed to obtain a transparent to translucent coating solution. Next, this coating solution is coated on at least one surface of a substrate such as a mirror or a transparent film by a coating method such as Bar Coat,
This is carried out at a temperature of 80 ° C or higher, preferably 120 ° C to 200 ° C.
By heating and drying within a temperature range of 1 ° C. for 1 minute or more, a first film composed of the first coating agent of the present invention is obtained. At this time, since the hydrophilic material does not require a base material, when the base material is removed from the hydrophilic material, the first coating agent and a film such as a PET film that does not adhere to the first coating agent,
The first coating agent may be coated, heated and dried, and then removed. Next, the components of the second coating agent are mixed to obtain a transparent to translucent coating solution. Then, the coating liquid is coated on the first coating, and the coating liquid is heated at a temperature of 80 ° C. or more, preferably 120 ° C.
By heating and drying in a temperature range of 1 to 200 ° C. for 1 minute or more, a second coating film composed of the second coating agent of the present invention is obtained. As a result, a hydrophilic material of a two-layer coat film composed of the first film and the second film is obtained. Further, the latter can be prepared by omitting the step of heating and drying the first coating agent. Here, the longer the heating and drying time is, the better, but since the optimum time varies depending on the heating method, it cannot be said unconditionally which one is better. Further, a step of forming a first coating on the surface of the base material without curing the first coating agent, and a step of applying the second coating agent thereon before being cured, and thereafter curing the second coating agent. After the method for producing a hydrophilic member and the step of forming the first coating with the first coating agent on the surface of the base material, before applying the second coating agent, A method for producing a hydrophilic member, comprising: a step of curing a coating agent to form a first coating; and a step of applying the second coating agent thereon and thereafter curing the coating. Is a production method in which the same operation as described above is performed except that the operation of removing the two-layer coat film or the three-layer coat film from the substrate is not performed in the same manner as described above. Then, by using such a method, a hydrophilic member in which a hydrophilic material that is a two-layer coating film or a three-layer coating film is coated on the base material can be obtained. Also, if necessary,
The heat treatment may be performed after coating the first coating liquid and / or the second coating liquid several times.

Further, in the first coating of the hydrophilic material having the two-coat coating or the three-coat coating, the surface on which the second coating or the third coating is not applied is further provided with: When a hydrophilic material having the same configuration as the second film or the third film and having a hydrophilic surface on both sides is produced, it may be produced in the same manner as the method for producing the hydrophilic material. it can. The same applies to the case of producing the double-sided hydrophilic member. Thereby, not only the hydrophilic material or the hydrophilic member can be provided with the function as the adhesive material as described above, but also the hydrophilicity or anti-fog property or the drip function on the surface opposite to the adhesive surface. It is possible to provide a hydrophilic material having

The hydrophilic member as the double-sided hydrophilic member includes:
It is also possible to use a hydrophilic member having the characteristics of a member with an adhesive. In the present invention, since the hydrophilic member is a member with an adhesive, when the member is attached to a mirror or glass, a hydrophilic surface having a drip function is used as an adhesive surface, and a liquid adhesive is used. By simply applying water to the surface to generate a water film without using it, the member can be firmly adhered to glass, a mirror, or the like to some extent. Therefore, for example, a member having a base material such as a PET film can be attached to glass. And the member with adhesive, like the above-mentioned adhesive, sandwiching air,
Since it is a hydrophilic member that has a feature that it can be easily attached without taking care of the displacement of the attachment position or the like, it can be used as a protective film or seal for a mirror that can be easily attached.

The hydrophilic member which is the double-sided hydrophilic member includes:
It is also possible to provide a hydrophilic member characterized in that both surfaces of the hydrophilic member are members with a double-sided adhesive having adhesive performance. In the present invention, since the hydrophilic member is a member with a double-sided adhesive material having adhesive performance on both sides, the hydrophilic member can be attached to a mirror or glass and simultaneously adhered to a surface opposite to the adhesive surface. It is possible to attach small pieces of glass to the glass or mirror to some extent by simply applying water and generating a water film without using an adhesive on the adhesive surface It has the feature of having a double-sided adhesive function.

The hydrophilic member as the double-sided hydrophilic member includes:
It is also possible to provide a hydrophilic member characterized in that one surface of the hydrophilic member is an adhesive having an adhesive property and the other surface is a hydrophilic material having a hydrophilic surface. In the present invention, one side of the hydrophilic member is an adhesive having an adhesive property,
Since the other surface is made of a hydrophilic material having a hydrophilic surface, not only the surface having the above-described adhesive property is imparted to the hydrophilic member, but also the surface opposite to the adhesive surface has hydrophilicity or protection. It is possible to provide a hydrophilic member having a cloudy or hydrophilic surface having a dropping function. In addition, when pasting it, the surface with hydrophilic performance can be made the front surface regardless of which side it is pasted, so it can be pasted without worrying about the front and back of the hydrophilic member, pasting operation Since no extra attention is required, the use of this can provide a convenient hydrophilic member that can be easily attached.

The coating method is not particularly limited, and any coating method such as bar coating, die coating, curtain flow coating, roll coating, gravure coating, multi-coating, comma coating, spray coating, spin coating, dip coating, etc. Can be used. Since the first coating agent can be coated by a curtain flow coat even on a veneer such as a mirror, coating can be quickly performed even on a veneer such as a considerably large mirror. Therefore, a curtain flow coat is preferred. The film thickness of the film obtained by this is not particularly limited, but in the case of the lower first film, 0.001 to
It is preferably 20 μm, more preferably 0.01 to 1 μm.
μm. However, the upper limit of the film thickness is not particularly limited, and it is good that the thicker the film thickness, the better the anti-fog performance is.However, due to mechanical characteristics, the thicker the film thickness, the more uneven the appearance. Because it becomes worse by
The above film thickness is appropriate. The thickness of the second upper coating is preferably 4 to 300 nm, more preferably 10 to 50 nm. The thickness of the third coat of the intermediate layer is preferably 0.001 to 20 μm, more preferably 0.005 to 1 μm.

The second coating film having a dropping function according to the present invention is formed by the following method. The particle diameter and particle shape of the hydrophilic inorganic oxide fine particles in the second coating agent, the mixing ratio of the carboxylic acid-containing compound to the inorganic oxide fine particles, Arithmetic average roughness (R) obtained by adjusting the partial concentration, the dispersion state of the inorganic oxide fine particles, and the like.
a) is 2 to 100 nm, and the average distance between irregularities (S
m) is preferably 4 to 300 nm.

[0130] In the present invention, a lower layer of the first coating,
Between the upper layer of the second coating, the inorganic binder may be coated, as the inorganic binder, the same zirconium compound and inorganic alkoxide used in the first coating agent are preferably used. .
The inorganic binder includes an OH group of the inorganic oxide in the second coating agent, an OH group of the carboxylic acid-containing compound, an OH group of the inorganic binder in the first coating agent, and water absorption. OH of functional organic polymer
A dehydration-condensation reaction occurs between the groups, and there is an effect that a hydrophilic material having high scratch resistance, which does not serve to strengthen the bond between the upper layer and the lower layer, can be produced.

In the present invention, a lower layer of the first coating,
Between the upper layer of the second coating and the upper portion of the upper layer, a surfactant may be further coated, and the surfactant is the same as that used in the first coating agent. Surfactants are preferably used. Then, this surfactant is coated between the upper layer and the lower layer, or is coated on a further upper portion of the upper layer, thereby improving the wettability of the upper layer and allowing the water to flow without scratching the coating. It is capable of exhibiting dropping properties and has an effect that it can be used even in places where it is difficult to remove water from the coating.

According to a preferred embodiment of the present invention, the contact angle of water of the hydrophilic material is 35 degrees or less. Thereby, when a water droplet adheres, a water film can be efficiently formed, and as a result, the flowability can be improved. Further, it is more preferable to set the contact angle of water of the hydrophilic material to 20 degrees or less because a rapid water film can be formed. In addition, with respect to dirt having relatively low polarity such as oily dirt generated from exhaust gas or the like, dirt can be easily removed with rainwater or the like if the contact angle is 35 degrees or less, and more preferably. 20 degrees or less.

Further, according to a preferred embodiment of the present invention, the contact angle of water of the hydrophilic material is set to 10 degrees or less. This allows
When water droplets adhere, a water film can be efficiently formed, and the moisture in the air spreads directly on the surface of the film as a water film, so that there is no unevenness on the film surface due to water droplets and the like, and as a result, the length is reduced. It has the effect of maintaining anti-fog properties over time.

In the present invention, a hydrophilic material which is a two-layer coating film or a three-layer coating film, or a hydrophilic member obtained by applying it to a substrate such as a mirror or a film is produced by the above-mentioned production method. As a result, the wettability of water due to the uneven shape of the droplet film surface as described above and the effect of reducing the contact angle of water droplets are added to the film, so that water is applied to the film to generate a water film. By doing so, an effect that the antifogging performance is maintained for a long time can be obtained as compared with an antifogging film having only a moisture absorbing film. And since the two-layer coating film and the three-layer coating film have both a first film having a moisture absorbing property and a second film having a drip performance, a bathroom mirror and a vanity mirror are provided. There is an advantage that an antifogging film that can serve both can be formed. Since the bathroom mirror is used in a bathroom where the structure is such that water or hot water can fall on the wall or floor, it is necessary to apply water necessary to generate a water film on the drip film. In addition, it is a convenient method in using a droplet coating without any hindrance. However, the droplet coating does not exhibit anti-fog performance unless water is applied, and is not suitable as a technique used for a vanity mirror in an environment where water cannot be applied. On the other hand, a moisture-absorbing film can exhibit anti-fog performance without water, and is an optimal technique in a low-humidity environment such as a bathroom, such as a bathroom. However, when this is performed in a bathroom, the moisture absorption film is quickly saturated because the bathroom is high in humidity, and the clouding starts to occur in a short time. Therefore, there is a disadvantage that the moisture absorbing coating cannot be used in a bathroom. As described above, both coatings have a problem that the place of use is limited. However, a two-layer coating or a three-layer coating in which both coatings are coated in two or three layers has the advantages of both coatings, so it is an anti-fog coating that can be used in both bathrooms and washrooms. Become. As described above, the two-layer coating film and the three-layer coating film are antifogging technologies that can be used as both a bathroom mirror and a vanity mirror.

When an antifogging film consisting of only a droplet film is used, a shampoo, a rinse,
Alternatively, when a chemical such as a conditioner adheres to the surface of the film, the film loses its drip property, and the portion repels water. However, in the case of the two-layer coating film or the three-layer coating film, washing with water for the chemical, or
Such chemicals can be washed away by simple washing by hand performed while scraping water, and there is an effect of easily recovering the dripping property. That is, the two-layer coating film and the three-layer coating film are characterized in that the chemical cleaning performance is higher than that of the other droplet coating films.

The reason why the use of the two-layer coating film or the three-layer coating film as described above can improve the chemical resistance as compared with the droplet coating film composed of an organic substance or an inorganic substance is as follows. This is probably because the coating or the three-layer coating has a structure that does not easily absorb silicone, which is one of the constituent components such as rinse. By the way, it is general that silicones are generally added to hair washing detergents such as shampoos, rinses and conditioners. Therefore, when the anti-fog film provided with the droplet coating is used in a bathroom mirror, the hair is washed in the bathroom, and when those chemicals are attached to the film, the film becomes like a hydroxyl group of silicone contained in a rinse or the like. The hydrophilic portion forms a hydrogen bond with the hydrophilic portion on the surface of the coating, and the silicone is difficult to remove from the coating. At the same time, since silicone has a hydrophobic portion such as alkoxide, it naturally adsorbs the hydrophobic portion on the opposite side of the coating, that is, outwards. The drip surface becomes hydrophobic. In particular, since the surface of a droplet coating film composed of an inorganic substance is porous, once such a component enters, there is a surface that cannot be easily removed even after washing. In addition, such a problem is described in
This is also true for a droplet film composed of an organic substance such as -107969. By the way, the coating does not have an uneven shape like a droplet coating film made of an inorganic substance, and even if a foreign substance such as silicone enters the coating, the foreign substance is easily removed and has a surface that is easy to clean. However, the coating is mainly composed of a hydrophilic portion and a hydrophobic portion coexisting, and it is difficult to separate when silicone is attached. Particularly, in the adsorption portion where the hydrophobic portions are hydrophobically bonded, it is difficult for water to enter the portion. However, a washing operation that applies a load to the coating, such as rubbing with a hand or a brush, is required without washing away with only water. Therefore, in the case of such a coating, some surface strength of the coating is required to remove the silicones from the coating.

On the other hand, in the case of the two-layer coating film or the three-layer coating film, the base of the droplet film is a moisture absorbing layer, and the moisture absorbing layer has a property of swelling when absorbing moisture. The shape of the irregularities changes according to the degree of absorption of water.For example, even if the silicone adheres to the recesses on the surface of the coating, the moisture is swelled on the adhering part to expand the moisture absorbing layer, and the silicone etc. Can be expanded into the concave portion into which the hydrophilic group of the silicone and the hydrophilic portion of the coating, or
This has the effect of forcibly separating the hydrophobic groups of the silicone from the hydrophobic groups of the silicone. Therefore, it is considered that the silicone is easily washed off. From this fact, it is considered that the coating can be easily cleaned even with silicones, and as a result, the chemical resistance of the coating is improved. In this way, by forming a two-layer coating film, a film having high chemical resistance can be obtained.

In the present invention, a two-layer coating film or a three-layer coating film is formed by using the first coating agent containing the inorganic binder to prepare a hydrophilic material. And, since the lower layer is a moisture-absorbing film having an organic-inorganic hybrid structure, the lower layer of the inorganic binder-containing two-layer coat film has a lower film surface strength than the two-layer coat film in which the lower layer is composed only of an organic substance. There is a feature that a high coating can be obtained. In addition, since the two-layer coating film has a higher film surface strength than the droplet coating film composed of an organic substance, shampoo, rinsing and the like are applied to the surface of the coating film as described above with water or hot water. Even if there is an adhering matter that cannot be removed only by scratching, it can be wiped off with a hand or a towel without worrying about damage to the film or deterioration in performance to some extent.

By the way, the upper layer droplet coating film constituting the two-layer coating film has a droplet-driving property for the above-mentioned reason, but the lower layer hygroscopic film is mainly used in the surrounding atmosphere. It is composed of a water-absorbing organic polymer capable of absorbing the moisture of an organic binder, and an inorganic binder serving as a spacer for preventing bonding between polymers or adhesion between polymers. By having a structure, even when water is absorbed by the coating, the coating is characterized by being a water-resistant or scratch-resistant coating that does not easily dissolve or break. In addition, since the binder serves as a spacer,
For example, there is a feature that it is possible to prevent a hydrogen bond due to an approach between hydroxyl groups in a polymer, to provide a void so that water or moisture easily enters the coating, and to improve the scratch resistance without lowering the moisture absorption performance. . Therefore, when a two-layer coat film is formed using the film having such a configuration as a lower layer, a film having both hydrophilicity and scratch resistance can be obtained.

In the two-layer coating film, the carboxylic acid-containing compound in the upper layer functions to bond the inorganic oxides or the inorganic oxide and the lower layer, and at the same time, to a high temperature and high humidity condition. This has the effect of suppressing the phenomenon of hydrophilic degradation. The main cause of the deterioration is considered to be the phenomenon of weathering occurring in glass or the like, and it is considered that the carboxylic acid-containing compound has an effect of suppressing this weathering. By the way, this phenomenon of weathering is due to the ion exchange between hydrogen ions of water adsorbed on the silica surface and alkali ions on the silica surface. It is a phenomenon that is produced and further reacts with carbon dioxide gas in the air to form a carbonate, which shows greater corrosiveness and corrodes the entire silica. The rate of this corrosion depends on the pH
It is said that each time the temperature increases by 1 or each time the temperature increases by 10 ° C., the temperature doubles.
It is thought that this corrosion spreads at a considerable speed. However, the carboxylic acid-containing compound ion-exchanges with alkali ions ionically bonded to silica in the coating solution before the coating film, and the alkali ions are formed in a state separated from silica, so that the film is formed. It is considered that the resulting film does not undergo weathering and becomes a coating film having a property of maintaining hydrophilicity even in a high temperature and high humidity condition.

The hydrophilic material is characterized by having a function as an adhesive. The adhesive used here means that the adhesive is adhered to the surface of a normally standing material such as a wall, a window, a door, or a mirror, and even if the material is pressed down to a certain extent from the surface of the material, the material may come off. A material that has an adhesive property that does not fall. In the present invention,
When the hydrophilic material is an adhesive, when the hydrophilic material is attached to a mirror or glass, a liquid adhesive is used by forming a hydrophilic surface having a drip function as an adhesive surface. Instead, the hydrophilic material can be firmly adhered to glass, a mirror, or the like to some extent simply by applying water to generate a water film. By the way, as described above, the method of attaching the adhesive is such that a water film is generated by applying water to an adhesive surface having a flow-drop function, and the water film surface is attached to a surface to be adhered such as a mirror. When the film no longer dries, it adheres through a process of firmly sticking. Therefore, when the adhesive surface of this adhesive material is stuck on a mirror or the like, air is hardly trapped between the mirror and the adhesive surface.
While the water film is present, the air can be easily removed by pushing the air out of the surface of the hydrophilic material with a finger. Furthermore, when pasting with an adhesive such as ordinary glue,
Attempting to correct the position or angle of the adhesive to be applied involves the trouble of peeling it off once, but in this method, the position and angle can be easily adjusted by shifting the water film while it is present. There is an advantage that can be corrected. From these facts, the hydrophilic material has a feature that it can be easily pasted without much care about air entrapment and displacement of the pasting position, and can be used as a protective film or a seal of a simple pasting mirror. is there. These functions as an adhesive also apply to a hydrophilic member.

Therefore, by using the two-layer coating film or the three-layer coating film as a base material such as a mirror or a film, the coating film has a drip-proof property that the anti-fog performance is maintained for a long time, and the surface strength of the coating film, that is, At the same time as the scratch resistance increases, even when a chemical such as a shampoo, a rinse, or a conditioner commonly used in a bathroom or the like adheres to the surface of the coating film as described above, the chemical is washed with water or the water is scraped. A chemical coating that can be easily washed off by simple hand washing performed while shaking, or a hydrophilic coating with chemical cleaning properties and a property that maintains hydrophilicity even under high temperature and high humidity conditions Can be.

In the present invention, since the inorganic binder is a zirconium compound, there is an effect that a coating solution having a higher defoaming performance can be prepared as compared with a silicon compound as another inorganic binder. Inorganic binders such as tetraethoxysilane, which is one of the silicon compounds, or the hydrolytic dehydration-condensation reaction product, cannot substitute all alkoxy groups even if they are hydrolyzed to substitute alkoxy groups with hydroxyl groups. Therefore, the alkoxy group remains in the coating liquid. In the case of such a liquid, when air is mixed, air is trapped in the hydrophobic group, and in the case of a liquid having a particularly high viscosity, it is difficult to remove bubbles, and as a result, mass production is performed by a coating machine. In such a case, there are many cases in which air bubbles are contained in the film, and only a film having a low yield can be formed. However, in the case of a zirconium compound, zirconium nitrate, which is one of the compounds, is converted into zirconium oxynitrate in air while being a salt, and in an aqueous solution, becomes zirconyl chelate to form hydroxyl groups in a water-absorbing organic polymer. The binder that binds to has a characteristic that changes naturally. Since there is no such thing as a hydrophobic group, there is an effect that the above problem does not occur.

In the present invention, in order to improve the adhesiveness between the upper layer and the lower layer, the first coating agent or
As an intermediate layer coated between the upper layer and the lower layer, an acrylic resin may be added or coated.

In the present invention, the acrylic resin refers to at least 60% by weight of alkyl esters of acrylic acid or methacrylic acid [hereinafter referred to as alkyl (meth) acrylates]. Or a mixture of monomers of alkyl (meth) acrylates and alkenylbenzenes and 0 to 40% by weight of a copolymerizable α, β-ethylenically unsaturated monomer. According to the conditions, for example, a polymer or copolymer obtained by emulsion polymerization in an aqueous medium in the presence of a surfactant. Examples of the alkyl (meth) acrylate used in the present invention include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, and acryl-n-ester.
-Butyl ester, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, methacrylic acid -2-ethylhexyl ester, decyl methacrylate, and the like. Generally, an alkyl acrylate having an alkyl group having 1 to 20 carbon atoms and / or
Alternatively, an alkyl ester of methacrylic acid having 1 to 20 carbon atoms in the alkyl group is used. The alkenylbenzenes used in the present invention include, for example, styrene, α-methylstyrene, vinyltoluene and the like. When a monomer composed of a mixture of such an alkenylbenzene and an alkyl (meth) acrylate is used, it varies depending on the amount of the α, β-ethylenically unsaturated monomer used. It is preferable that the use ratio of the alkyl (meth) acrylate is 10% by weight or more. The acrylic resin desirably contains alkenylbenzenes in a range of 70% by weight or less. The acrylic resin of the present invention has the above (meth)
When at least 60% by weight of a monomer composed of a mixture of alkyl acrylates or alkyl (meth) acrylates and alkenylbenzenes is contained, and when the amount is less than 60% by weight, forming coating is performed. The water resistance of the film is not sufficient, and the antifogging sustaining performance cannot be exhibited. Other copolymerizable α, β-ethylenically unsaturated monomers used to obtain the acrylic resin of the present invention include, for example, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid. Α, β such as itaconic acid
-Ethylenically unsaturated carboxylic acids, α, β-ethylenically unsaturated sulfonic acids such as ethylenesulfonic acid; 2-
Acrylamide-2-methylpropanoic acid; α, β-ethylenically unsaturated phosphonic acids; hydroxyl-containing vinyl monomers such as hydroxyethyl of acrylic acid or methacrylic acid; acrylonitriles; acrylic amides; glycidyl of acrylic acid or methacrylic acid Esters and the like. These monomers may be used alone or in combination of two or more, and may be used in the range of 0 to 40% by weight. 40% by weight
Exceeding this is not preferred because it reduces the antifogging performance.
The aqueous emulsion of the acrylic resin can be produced by a conventionally known emulsion polymerization method. For example, the monomer can be obtained by emulsion polymerization in an aqueous medium in the presence of a surfactant. As the surfactant used in producing the acrylic resin of the present invention, any of an anionic surfactant, a cationic surfactant, and a nonionic surfactant that can be added to the first coating agent. It may be.

According to the present invention, when coating the base material surface with the first coating agent, the base material surface is washed with a cleaning agent in advance to remove impurities on the base material surface,
The hydrophilicity of the substrate can be enhanced. And thereby, a bubble with high adhesion can be obtained without air bubbles entering between the substrate and the coating.

The term “washing” as used herein refers to degreasing washing for removing foreign substances adhering to a substrate, such as cleaning with chlorofluorocarbon, isopropanol, ethanol, sodium hydroxide, a neutral detergent, or the like, or sandpaper or the like. Refers to a physical treatment for the purpose of polishing, increasing the smoothness of the substrate surface, and lowering the surface tension. For example, in the case of coating the mirror with the first coating, the washing by ceria polishing is suitable as the washing. This is a method of dissolving particles mainly composed of ceria in a neutral detergent, etc. to make a detergent, and then washing the substrate surface, thereby degreasing and smoothing the substrate surface, and improving hydrophilicity by reducing surface tension. Can be achieved.

In the present invention, as described above, by pre-hydrophilizing, the wettability of the base material is improved, a clean film can be formed, and a film having high adhesion can be obtained.

For the above-mentioned hydrophilization, chemicals, ultraviolet rays, radiation,
Oxidation of the substrate surface by discharge or the like is considered as a method. Among them, particularly, when the substrate is subjected to a corona discharge treatment and then coated with a coating liquid, the hydrophilicity of the substrate is higher than in other cases. The performance is further improved, and a clean film can be formed, and a film having high adhesion can be obtained. Particularly effective when used in combination with ceria polishing.

This is because corona discharge on the surface of the base material causes high-speed and low-speed electrons in the air gap to collide with oxygen atoms to generate excited oxygen molecules, thereby producing ozone, highly reactive oxygen atoms, and free radicals. To change. The active species can oxidize the surface of the base material and improve the wettability of the coating liquid. By modifying the surface of the base material in this manner, the adhesion between the first coating agent, which is another polar molecule, and the base material can be promoted, and as a result, the adhesion can be improved. it can.

In preparing the hydrophilic member, the substrate on which the first coating agent can be applied is not particularly limited, and examples thereof include metals, ceramics, glass, plastic, wood, stone, cement, concrete, and fibers. , Fabric,
Combinations thereof and their laminates can be suitably used. The substrate may be determined in consideration of the use of the hydrophilic member. Then, the transparent base material of the glass or plastic among them becomes a transparent hydrophilic member because the surface of the obtained hydrophilic material is also transparent.

The hydrophilic member using a mirror as the substrate is as follows:
Mirror made of glass substrate with reflection coating on back surface, mirror made of transparent plastic with reflection coating on back surface, mirror with plastic, glass, metal, etc. A mirror with a reflective coat on the surface of a base material such as a mirror and a transparent hard coat on it, a mirror made of a mirror-polished metal base, and a transparent hard coat on the mirror made of a mirror-polished metal base And a mirror provided with a transparent hard coat on a transparent plastic base material provided with a reflective coat on the back surface can be suitably used as the base material. The hydrophilic member using a transparent plate-shaped member as the base material, polyethylene terephthalate,
A plastic member such as polyvinyl chloride or methacrylic resin, or a plate glass such as soda-lime glass, borosilicate glass, or aluminosilicate glass can be suitably used as the base material. As the hydrophilic member using a transparent lens as the base material, polyethylene terephthalate, polyvinyl chloride, a plastic member such as methacrylic resin, or a glass such as soda-lime glass, borosilicate glass, aluminosilicate glass, etc. It can be suitably used as a substrate. As the hydrophilic member using a transparent film as the base material, a member formed by processing a thermoplastic resin into a film shape is usually used as the base material. As the thermoplastic resin here, polyolefin resin, polyvinyl chloride, vinyl chloride-methyl methacrylate copolymer,
Chlorine resins such as polyvinylidene chloride, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, and fluorine resins are preferably used. Examples of the polyolefin resin include α-olefin homopolymers and copolymers of α-olefins as main components with different kinds of monomers, such as polyethylene, polypropylene, ethylene-butene copolymer, and ethylene-olefin. 4
-Methyl-1-pentene copolymer, ethylene-α-olefin copolymer such as ethylene-hexene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymer , Ethylene-vinyl acetate-methyl methacrylate copolymer,
An ionomer resin and the like can be mentioned. The substrate is not limited to the above substrate. A transparent intermediate layer may be provided between the substrate and the lower layer for the purpose of improving adhesion to the substrate and the like.

The hydrophilic mirror, which is a hydrophilic member using a mirror as a base material according to the present invention, can be used for an automobile side mirror, an automobile room mirror, a mirror installed in a bathroom or a washroom, and the like. In particular, considering the drip performance of the hydrophilic material of the present invention, it is easy to generate water film by scratching the water locally, and the steam of hot water easily adheres to the surface and easily becomes cloudy. .

The hydrophilic transparent plate-shaped member, which is a hydrophilic member using a transparent plate-shaped member as the base material, includes a window glass for a house, a glass for furniture, a window glass for an automobile, a glass for an instrument of an automobile, and the like. Can be used for Further, as the hydrophilic transparent lens which is a hydrophilic member using a transparent lens as the base material, glasses, goggles, camera lenses,
It can be used for a lens of a portable video camera, a lens for an astronomical telescope, and the like. Further, as a hydrophilic transparent film which is a hydrophilic member using a transparent film as the base material, it is applied to a wrapping paper for food, a side mirror for an automobile, a room mirror for an automobile, a mirror installed in a bathroom or a washroom. It can be used for anti-fog films and the like. In addition, the base material may be any of a ceiling material for a bathroom having antifouling properties and dewproofing properties, a pipe for a toilet, a pipe for water supply, a urinal, a toilet, a trap for a toilet, a wash bowl, and a wash trap. It can be suitably used. Further, the base material is an antifouling, dewproofing bathtub, bathroom wall material, bathroom flooring material, bathroom grating, shower hook, bathtub handgrip, bathtub apron section,
Bathtub drain plugs, bathroom windows, bathroom window frames, bathroom window floorboards, bathroom lighting fixtures, drainage plates, drainage pits, bathroom doors, bathroom door frames, bathroom window bars, bathroom door bars, floorboards, mats, Soap rest, pail, bathroom mirror, bath chair, transfer box
, Water heaters, bathroom storage shelves, bathroom handrails, bath lids, bathroom towel rails, shower chairs, basins, etc. bathroom components, kitchen kitchen backs, kitchen flooring, sinks, kitchen counters , Drain baskets, dish dryers, dishwashers, stoves, range hoods, ventilation fans, stove ignition parts, toilet flooring, toilet wall materials, toilet ceilings, ball taps, water taps, cigarette rolls, toilet seats , Elevator seat, toilet door,
Toilet members such as toilet bath keys, toilet towel rails, toilet lids, toilet railings, toilet counters, flush valves, toilet bowl hakama, urinal wall surfaces, tanks, flushing nozzles for toilet seats with a cleaning function, Wash basin, wash basin, wash basin, storage bin, drain plug, toothbrush stand, wash basin lighting fixture, wash counter, water soap dispenser, wash basin, mouth washer, hand dryer, washing tub, washing machine lid, Suitable for washing machine pan, dewatering tub, air conditioner filter, touch panel, faucet fitting, cover of human body detection sensor, shower hose, shower head, shower water discharge section, sealant, joint Available to

The above method of use can be used even in the case of a hydrophilic material having no base material.

Further, these methods of use can be applied to the above-mentioned hydrophilic material or hydrophilic member having hydrophilicity on both surfaces. And a hydrophilic member using a transparent film as the base material, or a hydrophilic material having double-sided hydrophilicity, or a toilet bowl hatch which is one of the methods of using a hydrophilic member having double-sided hydrophilicity. Utilization of the urinal on the wall has a surface that makes it possible to prevent dew condensation on the wall of the urinal.

In the present invention, the high-humidity zone includes a kitchen, a washroom, a bathroom, a toilet, a hot-water supply room, a clog box,
In houses or non-houses such as entrances, closets, cupboards, rooms with washing machines, around gas stoves, etc., it refers to zones where the relative humidity becomes 50% or more depending on use conditions, where hydrophilic materials and hydrophilic materials are used. A characteristic member is used.

Further, in the present invention, the first coating agent and the second coating agent are each packed in a bottle with a lid, and a coating liquid or a set of them is set.
As a coating agent, brush and anywhere you like,
Apply with a brush, apply the coating liquid by infiltrating it into a foam or non-woven cloth, put a coating liquid in a bottle, and set up a mechanism that allows the liquid like a non-woven cloth to seep into the opening of the bottle, and apply the liquid There is an effect that coating can be performed by a method such as a stretching method. Then, as a method of drying and curing, a hydrophilic material or a hydrophilic member can be prepared by natural drying or drying with a home drier. And, as described above, depending on the method of drying the first coating agent and the second coating agent, it is possible to separately produce the two-layer coating film and the three-layer coating film. Further, the set of the coating liquid filled in the bottle with the lid can be set in a coating machine for mass production, and the base material can be coated by a desired coating method. Therefore, this coating set has the effect of performing coating regardless of the place of use by performing the above-mentioned method of use. Also,
Depending on the base material to be applied, the same ability as the two-layer coat film and the third coat film can be obtained only by directly applying the second coating agent. The container of the coating set, the method for applying, and the tool are not limited to those described above.

Further, the hydrophilic transparent film has a structure in which a part without a film is intentionally formed on the film by using the dripping property and the part becomes cloudy when placed in a high humidity environment. To And that cloudy place,
For example, company names, company or product logos, character designs, school badges, company badges, all kinds of design patterns and characters, so that they become characters that appear when the anti-fog film becomes cloudy Can also be made.

Also, a transparent inside pig is provided in the electric refrigerator so that the inside can be seen without opening the inside of the refrigerator.
When opening the refrigerator door, make the structure so that the cool air in the refrigerator escapes and the freshness of the food in the refrigerator does not fall.Affix an anti-fog film on the transparent inside pig, or apply a hydrophilic coating on the door itself. By coating, it is also possible to make a product that is designed to prevent the middle pig from fogging.

[0161]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The evaluation methods used in the examples and comparative examples are as follows. Hereinafter, the solution of the first composition or the second composition obtained in the examples is referred to as a coating liquid, and the hydrophilic material obtained thereby is referred to as a sample.

Chemical Cleaning Performance (Rinse) Evaluation Method 1; Supe
One drop of r Mild (manufactured by Shiseido) is dropped on the surface of the coating using a disposable 2 ml disposable dropper. After standing for 1 hour in an atmosphere of 25 ° C., the solution is poured off with a neutral detergent water, and the dropping performance of the portion is examined. The droplet performance was measured using a sample film of 50 mm *.
Affix it to a 100 mm square mirror, cool the mirror to 5 ° C, scrape the water, stand it up at 40 ° C and 100% RH, stand still, and 1 minute after scraping the water Blow on the scratched surface to see if it is cloudy or not. ；: No clouding even when breathing on the trace. ×; cloudy when blowing on the trace.

Chemical cleaning performance (rinse) evaluation method 2: Supe
One drop of r Mild (manufactured by Shiseido) is dropped on the membrane surface with a disposable 2 ml disposable dropper, left for 1 hour in an atmosphere of 25 ° C., then washed away with a neutral detergent water, and the appearance of the trace is examined. The appearance is evaluated by visually confirming the presence or absence of a flaw. ；: No scratch or peeling is observed on the trace. ×: There are scratches and peeling at the marks.

Initial anti-fogging performance evaluation method;
The coated sample is placed in a% atmosphere and the time required for haze to cover half of the entire film surface is measured. At this time, the sample is left in a refrigerator at 5 ° C. for 30 minutes and then measured. ；: Time until clouding is 2 minutes or more. Δ: Time until clouding is 30 seconds or more and 2 minutes or less. ×: Time until clouding is 30 seconds or less.

Droplet performance evaluation method: A sample coated with a coating is placed in an atmosphere of 30 ° C. and 100% humidity, and the time required for clouding to cover half of the entire film surface is measured. At this time,
The sample was left in a refrigerator at 5 ° C for 30 minutes,
Measure. Immediately before performing this evaluation, a water film is generated by spraying. ；: Time until clouding is 3 minutes or more. Δ: Time until clouding is 30 seconds or more and 3 minutes or less. ×: Time until clouding is 30 seconds or less.

Evaluation of Initial Appearance The appearance of the sample is visually inspected. A: No air bubbles or turbidity was observed on the film surface. ；: The film surface has only a small amount of air bubbles or cloudiness that does not matter. Δ: Some bubbles and cloudiness are observed on the film surface. X: Air bubbles and cloudiness are quite conspicuous on the film surface.

Evaluation of Water Resistance The sample coated with the film was immersed in water at room temperature for 30 seconds, and the surface of the film was rubbed with a tip of a squeegee (small spatula made of plastic) for 50 reciprocations. After drying in a normal temperature atmosphere, the rubbing marks were observed and evaluated. A: No scar is observed on the film surface, and the film has a drip property (in the case of a moisture-absorbing film, the initial antifogging property is 1 minute or more). ；: No scar was observed on the film surface, but there was a part without a droplet property (in the case of a moisture-absorbing film, one having an initial antifogging property of 1 minute or more). Δ: No scar was observed on the film surface, but there was no dripping property (in the case of a moisture-absorbing film, the initial antifogging property was 1 minute or more). ×: Scars are observed on the film surface, and the droplets are drip (in the case of a moisture absorbing film,
Without initial antifogging property for 1 minute or more).

Evaluation of Coating Strength The sample coated with the coating was subjected to 25 ° C., 40-60% RH.
After being left for 3 hours or more in the atmosphere described above, a pencil scratch value of the coating surface is measured, and the film strength is evaluated based on the measurement result. The evaluation was performed by the method described in the measurement of pencil scratch value specified in JIS K5400.

Evaluation by Color Difference (ΔE) Measurement The degree of discoloration of the surface of the sample on which the coating was applied was determined to be
Color Measuring System (Nippon Denshoku Industries Co., Ltd.)
Then, the color difference (ΔE) of the sample surface is measured. Standard of evaluation by ΔE. ◎; ΔE <1; level of film discoloration with no discoloration. ；; 1 ≦ ΔE <2; when compared with a member having no coating, it was found that the coating was slightly discolored, but the level of discoloration of the coating did not matter for practical use. Δ: 2 ≦ ΔE <3: Level of film discoloration in which discoloration is slightly anxious. ×; 3 ≦ ΔE; level of film discoloration in which discoloration is considerably remarkable.

Evaluation of Defoaming Performance of Bubbles in Coating Solution When coating is carried out by putting the coating solution into a coating machine for mass production such as a curtain coater,
In some cases, bubbles easily enter into the coating liquid, or once the coating liquid enters, it is difficult to remove. In this case, a bad appearance may occur such that bubbles remain in the film after coating, and therefore, a foam having an antifoaming action that easily removes bubbles even when the coating liquid is used is required. Estimate of defoaming action Put 80ml of coating liquid into 100ml beaker,
In addition, put a stirrer of 2cm length and 3mm width class,
Turn the knob to 10 memory units with the multiple magnetic stirrer F-606N (manufactured by Endo Kagaku Co., Ltd.)
Stir for a minute. After stirring, check if bubbles have escaped from the liquid. A state in which no bubbles have entered after stirring. △: After stirring, bubbles are contained, but all are removed within 10 seconds. ×: A state in which bubbles are formed after stirring and the bubbles are not removed even after 30 minutes.

Evaluation of Possibility of Corrosion of Pipe due to Coating Liquid When coating the coating liquid with a coating machine or the like, even in the case of stainless steel pipe, there is a possibility that the pipe and other contacting metal parts are corroded. Therefore, a problem may occur in the durability of the machine used. Then, 80 ml of the coating liquid is put into a 100 ml beaker, and stainless steel (SUS304) having a length of 5 cm, a width of 2 cm and a thickness of 2 mm is put therein and kept for one week. One week later, the appearance changes are observed. Estimation of the possibility of corrosion of pipes caused by coating liquid; no change in appearance, and can be applied with a normal coating machine. ×: Change in appearance was observed, and painting with a normal coating machine was not possible.

Evaluation of Adhesion by Crosscut Tape Method (Moisture Resistance Test) The sample coated with the film was soaked in warm water at 60 ° C. for 3 hours, and then soaked in normal temperature water for 16 hours. After drying, a test was conducted to check the adhesion of the coating to the substrate by the cross-cut tape method. The evaluation method is JIS K54
The test was performed by the method described in the crosscut tape method, which is a test for observing the adhesion of the paint general test method specified in 00. A: No peeled portion was observed on the film surface. ；: Less than 10 out of 100 peeled portions on the film surface. Δ: 10 to 20 out of 100 peeled portions on the film surface. ×: 20 or more out of 100 peeled portions on the film surface.

Measurement of Contact Angle with Water Drop on Coating Surface The measurement of the contact angle with water droplets on the coating surface was performed on a sample which had been left in a room at 20 ° C. and 45% RH for 1 hour or more after preparation. -X150 type, manufactured by Kyowa Interface Science Co., Ltd.).

Chemical Cleaning Performance (Shampoo) Evaluation Method 3: Merit (Made by Kao)
After applying 2 g to a 5 × 10 cm sample immersed in pure water for 0 minutes, the sample is dried at 40 ° C. for 15 minutes. This series of operations was repeated seven times. The surface was wet when a 1 wt% aqueous solution of shampoo was applied. Then, after repeating 7 times, the sample was washed with a tap water shower (water discharge 8 L /
), Washed with running water for 1 minute, dried at 40 ° C. for 10 minutes, and evaluated for antifogging.

Chemical Cleaning Performance (Rinse) Evaluation Method 4: Supe
r Mild (made by Shiseido)
After applying 2 g to a 5 × 10 cm sample immersed in pure water for 0 minutes, the sample is dried at 40 ° C. for 15 minutes. This series of operations was repeated seven times. The surface was wet when a 1 wt% aqueous solution of rinse was applied. Then, after repeating 7 times, bath magic phosphorus was applied to the sample surface until the sample could be covered, and the sample was allowed to stand for 3 minutes. Thereafter, the sample was washed with running water for 1 minute with a tap water shower (water discharge 8 L / min), dried at 40 ° C. for 10 minutes, and evaluated for anti-fogging.

Evaluation of Scratch Resistance Performance by Sliding Test The sample coated with the film was fixed to a sliding test device with cellophane tape, and a 500 g load, 11 cm × 7 cm contact area was applied to the sample while applying a three-fold dilution of bath magic phosphorus. A sliding test was performed in which a urethane sponge having a gripper was reciprocally slid 300 times. Then, the sample was washed with water and sufficiently dried, and then the anti-fogging area was measured by an anti-fogging evaluation device to evaluate the anti-fogging.

Evaluation of high-temperature and high-humidity resistance 1 A sample coated with a film was subjected to temperature: 40 ° C., humidity: 1
After leaving it to stand in an atmosphere of 00% RH for 12 hours and drying it sufficiently, the anti-fogging area was measured by an anti-fogging evaluation device, and the anti-fogging evaluation was performed.

Evaluation of high-temperature and high-humidity resistance 2 The sample coated with the coating was subjected to a temperature of 40 ° C., a humidity of 7
After allowing to stand in an atmosphere of 5% RH for 12 hours and sufficiently drying, the anti-fogging area was measured by an anti-fogging evaluation device, and the anti-fogging evaluation was performed.

Here, the evaluation apparatus and the evaluation method used in the present invention will be described in detail. Anti-fogging evaluation device: small glass tank (size / width 315 x depth 185 x height 2
44mm, manufactured by Nisso Corporation) into a large glass tank (size / width 590 x depth 290 x height 358 mm)
(Manufactured by Nisso Corporation). A mirror was attached to the inside of a small glass aquarium to circulate cooling water. Cooling water is a circulation type thermostatic water circulation device (TRL-C20, Thomas Kagaku
(Manufactured by Co., Ltd.). 2 inside the large glass tank
Humid air at 5 ° C. to 30 ° C. and 95% relative humidity was introduced.
The humid air was generated by a temperature and humidity generator and supplied by an air pump. Both small and large glass aquariums were covered. The lid was not sealed so that the humid air supplied into the large glass tank could be exhausted. Here, the temperature / humidity generator means an air pump (FX-7000ST, ENOMOTO MICRO).
PUMP MFG. Co. LTD. Made, maximum flow rate 80
L / min at a maximum pressure of 294.1 kPa) is supplied to a mass flow controller (model 3660 and CR-
(KOFLOC 300, manufactured by Kofloc Co., Ltd.) and controlled to 16 liters / minute, introduced into a humidifier, and bubbling to generate humidified air. Here, the humidifier is 28 cm x
It is a device that generates a humidified air by installing a container filled with pure water in a constant temperature water tank of 34 cm × 30 cm, introducing air into the container and bubbling. At this time, in order to easily generate humidified air, the temperature of the constant temperature
Constant temperature water circulation device set at 4.6 ° C (TRL-C20, Thomas
The temperature of the humidified air was adjusted to 2
Adjusted to 5 ° C.

Antifogging evaluation method: 20
A 10 cm × 5 cm droplet anti-fog film to be evaluated was stuck to the surface of a small glass water tank adjusted to a temperature of ° C. with water. Supplying humid air into a large glass water tank
The environment was 30 ° C. and 95% relative humidity. Ion-exchanged water was applied to the surface of the film using a polypropylene wash bottle to form a water film on the film surface, and the antifogging area after standing for 10 minutes was examined. Evaluation standard of anti-fogging area When 90% or more of a 10 cm × 5 cm sample does not fog; 〇 When the non-fogging area of a 10 cm × 5 cm sample is less than 90%;

Sliding test: Sliding test device (WASHABI)
LITY TESTER, manufactured by TOYOSEIKI). Bath magic phosphorus 3
500g load, 11cm x 7cm while applying double dilution
Slid 300 times with a urethane sponge (Scotch Bright, 3M, size) having a contact area with the sample. The sample after sliding is a tap water shower (water spouting 8L /
), Washed with running water for 1 minute, dried at 40 ° C., and evaluated for antifogging.

High-temperature and high-humidity test: Ion-exchanged water was placed in a 1-liter polypropylene beaker to a water depth of about 1 cm, a 5 × 10 cm sample was stuck on a 5 × 10 cm glass plate, and the sample was leaned on it and covered with Saran wrap. Heating dryer kept at 40 ° C while sealing with rubber bands:
ESPEC CONVECTION OVEN LC-
113 (TABAI ESPEC CORP, AC1
00V 1φ 60Hz, MAX. 11A, 40-25
0 ° C, HEATER 1.0kW, dryer internal volume W45
× H45 × D45 cm) for 12 hours, and then evaluated for antifogging.

[0183]

[Example 1] PVA-11 which is a polyvinyl alcohol
7H (average degree of polymerization: 1700, complete saponification type; degree of saponification: 99.3% or more) (manufactured by Kuraray); 5 g in water; 95 g
And stirred at 90 ° C. for 5 hours to dissolve PVA117H. (Hereinafter referred to as A1 liquid).
The test solution is applied to the side coated with a primer of PET film HSt74 (manufactured by Teijin) using a bar coater RD for testing.
It is coated with S03 (manufactured by Yoshimitsu Seiki Co., Ltd.), dried by heating at 145 ° C. for 4 minutes in an oven (DK-400, manufactured by Yamato Scientific Co., Ltd.), and the lower layer is coated on the PET film. Then, 10 g of L (+)-tartaric acid (manufactured by Wako Pure Chemical)
1.5 g of a 10% ethanol solution of tartaric acid obtained by dissolving in 90 g of primary ethanol (manufactured by Wako Pure Chemical Industries) is mixed with 1.5 g of colloidal silica ST-OUP (manufactured by Nissan Chemical Industries, Ltd.). The solution is first-grade ethanol (Wako Pure Chemical Industries) 2
Dissolve in 0 g to make a solution for the upper layer. Then, this solution is coated on the lower layer with a test bar coater RDS03 (manufactured by Yoshimitsu Seiki Co., Ltd.) and dried by heating at 145 ° C. for 4 minutes to obtain a transparent two-layer coating film in which the upper layer is coated on the lower layer. .

[0184]

Example 2 Zirconyl nitrate dihydrate (manufactured by Wako Pure Chemical Industries);
After adding 13 g and 87 g of water and stirring for 5 minutes, 60 g of ion exchange resin WA-20 (manufactured by Mitsubishi Kasei) is mixed in, and the mixture is stirred until the solution becomes pH 3.0. Thereafter, the solution and the ion-exchange resin are separated by decantation and allowed to stand at room temperature (25 ° C.) for one day. (Hereinafter referred to as A2 solution.) Then, 40 g of this A2 solution and 60 g of A1 solution, citric acid (manufactured by Wako Pure Chemical Industries); 20 g of distilled water; 1 g, distilled water; 20 g, and 10 g of primary ethanol (manufactured by Wako Pure Chemical Industries, Ltd.). (This solution is hereinafter referred to as solution C1.) Then, after stirring this solution C1 for 30 minutes,
Take 30 g, add 30 g of distilled water; stir and add C1
Make a C2 solution, which is a two-fold dilution of the solution. And this C2
A sample is prepared in the same manner as in Example 1 except that the liquid is used as a lower layer coating liquid instead of the A1 liquid of Example 1.

[0185]

Comparative Example 1 The C2 liquid of Example 2 was replaced with a PET film H
The side coated with the primer of St74 (manufactured by Teijin) is coated with a test bar coater RDS03 (manufactured by Yoshimitsu Seiki Co., Ltd.), dried by heating at 145 ° C. for 4 minutes, and coated with the C2 liquid on the base film. Thus, a transparent single-layer coating film is obtained.

[0186]

[Comparative Example 2] Sodium dodecylbenzenesulfonate ("Nurex Powder F" manufactured by NOF Corporation,
A 2% aqueous solution of (anionic) is prepared as a C3 solution for the upper layer. Then, on the film obtained in Comparative Example 1, the above C3
The solution was coated with a test bar coater RDS03 (manufactured by Yoshimitsu Seiki Co., Ltd.) and dried by heating at 145 ° C. for 4 minutes to obtain a transparent two-layer coating film in which the C3 solution was coated on a film as a substrate.

[0187]

[Table 1]

As shown in Table 1, it can be seen that the two-layer coating film is an anti-fogging film having high chemical detergency and high film surface strength, and also has high initial anti-fogging performance and drip performance.

[0189]

Example 3 PVA-11 which is a polyvinyl alcohol
0 (average degree of polymerization: 1000, complete saponification type; degree of saponification:
98% or more) (manufactured by Kuraray); 7 g, water; 93 g,
Stir at 90 ° C. for 5 hours to dissolve PVA110. Next, 13 g of zirconyl nitrate dihydrate (manufactured by Wako Pure Chemical Industries); 87 g of water were added, and the mixture was stirred for 5 minutes, and then ion-exchange resin WA-20 (manufactured by Mitsubishi Kasei); 60 g And stir until the solution has a pH of 2.5. Thereafter, the solution and the ion-exchange resin are separated by decantation and allowed to stand at room temperature (25 ° C.) for one day. (Hereinafter referred to as A4 solution) and this A4 solution;
3.5 g and A3; 6.4 g of liquid, 10 g of citric acid (manufactured by Wako Pure Chemical Industries); 10 g obtained by dissolving with 90 g of distilled water.
% Citric acid aqueous solution (hereinafter referred to as solution B2); 0.16
g, distilled water; 36 g, primary grade ethanol (Wako Pure Chemical Industries) 3
Mix 6 g each. (Hereinafter, this solution is referred to as C4 solution.) Then, this C4 solution is used as a PET film, HSt74.
On the side coated with (Teijin) primer,
Coat with YBA-1 type Baker applicator (Yoshimitsu Seiki Co., Ltd.) scale 1 and oven (DK-
400, manufactured by Yamato Scientific Co., Ltd.) and dried at 145 ° C. for 10 minutes to coat the lower layer on the PET film. Then, 10 g of citric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 90 g of distilled water; 18 g of a 10% aqueous citric acid solution obtained, and colloidal silica PL-3 (Fuso Chemical Industry) diluted to 10% with distilled water. 5 g of aluminum sol 10 (manufactured by Kawaken Fine Chemical Co., Ltd.) and 4 g of aluminum sol 10 were mixed, and the solution was dissolved in 58 g of distilled water (manufactured by Wako Pure Chemical Industries, Ltd.) to form a solution for the upper layer or an upper layer solution. Further, the solution is adjusted to pH 1.78 with nitric acid, and then stirred in an atmosphere at 65 ° C. for 12 hours. The solution is coated on the lower layer with a test bar coater RDS12 (manufactured by Yoshimitsu Seiki Co., Ltd.) and dried by heating at 145 ° C. for 10 minutes to obtain a transparent two-layer coating film coated on the film. .

[0190]

Example 4 In preparing the upper layer liquid of Example 3, 5 g of colloidal silica PL-3 (manufactured by Fuso Chemical Co., Ltd.) diluted to 10% with distilled water and 4 g of aluminum sol 10 (manufactured by Kawaken Fine Chemical Co., Ltd.) Was added, and instead, PL-3 in which colloidal silica was diluted to 10% with distilled water was used.
A transparent two-layer coating film coated on a film can be obtained by following Example 3 except that 9 g (manufactured by Fuso Chemical Industry Co., Ltd.) is added.

[0191]

COMPARATIVE EXAMPLE 3 A 10% aqueous citric acid solution in the preparation of the upper layer solution of Example 3; without adding 18 g, instead of distilled water;
By following the procedure of Example 3 except that 18 g is added, a transparent two-layer coating film coated on the film is obtained.

[0192]

COMPARATIVE EXAMPLE 4 A 10% aqueous citric acid solution in the preparation of the upper layer solution of Example 4; without adding 18 g, distilled water instead;
A transparent two-layer coating film coated on a film is obtained by following the procedure of Example 4 except for adding 18 g.

[0193]

[Table 2]

As shown in Table 2, the two-layer coating film obtained by adding a carboxylic acid-containing compound to the second coating agent is a hydrophilic film having high chemical detergency and high surface strength, and has an initial antifogging property. It can be seen that the droplet performance, the high temperature and high humidity resistance, and the scratch resistance are high.

[0195]

Example 5 PVA-11 which is a polyvinyl alcohol
0 (average degree of polymerization: 1000, complete saponification type; degree of saponification:
98% or more) (manufactured by Kuraray); 7 g, water; 93 g,
Stir at 90 ° C. for 5 hours to dissolve PVA110. Next, 13 g of zirconyl nitrate dihydrate (manufactured by Wako Pure Chemical Industries); 87 g of water were added, and the mixture was stirred for 5 minutes, and then ion-exchange resin WA-20 (manufactured by Mitsubishi Kasei); 60 g And stir until the solution has a pH of 2.5. Thereafter, the solution and the ion-exchange resin are separated by decantation and allowed to stand at room temperature (25 ° C.) for one day. (Hereinafter referred to as A6 solution) and this A6 solution; 1
3.8 g and A5; 19.2 g of a liquid, 1 g obtained by dissolving 20 g of citric acid (manufactured by Wako Pure Chemical Industries) with 180 g of distilled water.
0% citric acid aqueous solution (hereinafter referred to as B3 solution); 0.4
8 g, distilled water; 108 g, primary ethanol (manufactured by Wako Pure Chemical) 108 g, potassium sulfate (manufactured by Wako Pure Chemical); 2.5 g
Is dissolved in 97.5 g of a 2.5% aqueous solution of potassium sulfate; 2.4 g of each is mixed. (This solution is hereinafter referred to as C5 solution.) Then, this C5 solution is
On the side of the film coated with the primer of HSt74 (manufactured by Teijin), coat with a scale 1 of YBA-1 type Baker Applicator (manufactured by Yoshimitsu Seiki Co., Ltd.) and use an oven (DK-400, manufactured by Yamato Scientific Co., Ltd.). 145
Heat and dry at 10 ° C. for 10 minutes to coat the lower layer on the PET film. And 20 g of citric acid (manufactured by Wako Pure Chemical Industries)
Was dissolved in 180 g of distilled water; 110 g of a 10% aqueous citric acid solution obtained, and 30 g of colloidal silica PL-3 (manufactured by Fuso Chemical Industry Co., Ltd.) diluted to 10% with distilled water.
And aluminum sol 10 (manufactured by Kawaken Fine Chemical Co., Ltd.)
24 g, magnesium nitrate hexahydrate (manufactured by Wako Pure Chemical Industries);
5 g of distilled water; 5 g of an aqueous solution of 5% magnesium nitrate hexahydrate obtained by dissolving with 95 g; 5 g are mixed, and the solution is dissolved in 90 g of distilled water (manufactured by Wako Pure Chemical Industries), and a solution for the upper layer or Then, an upper layer solution is prepared, and the solution is adjusted to pH 1.78 with nitric acid, and then stirred in an atmosphere at 65 ° C. for 12 hours. The solution is coated on the lower layer with a test bar coater RDS12 (manufactured by Yoshimitsu Seiki Co., Ltd.) and dried by heating at 145 ° C. for 10 minutes to obtain a transparent two-layer coating film coated on the film. .

[0196]

EXAMPLE 6 In preparing the upper layer solution of Example 5, 5 g of magnesium nitrate hexahydrate aqueous solution was not added, and instead, 5 g of primary aluminum sulfate (manufactured by Kishida Chemical) was used.
Was dissolved in distilled water; 95 g of a 5% aqueous solution of aluminum sulfate obtained in the same manner as in Example 5 except that 5 g was added to obtain a transparent two-layer coating film coated on the film.

[0197]

Comparative Example 5 In the same manner as in Example 3, a transparent two-layer coating film coated on the film was obtained.

[0198]

[Table 3]

As shown in Table 3, the coating in which potassium ion was added to the first coating and magnesium ion was added to the second coating was a hydrophilic material having high chemical detergency and high coating surface strength. It can be seen that the drop performance, high temperature and high humidity resistance, and scratch resistance are high.

[0200]

According to the above method, a first coating agent or a second coating agent is prepared and coated on a base material, or the first coating obtained by the first coating agent is used as a base material. By creating a two-layer or three-layer coating, the coating surface strength and chemical cleaning performance are high,
It is possible to produce a hydrophilic material having not only good anti-fog performance, drip property, appearance and the like, but also high resistance to high temperature, high humidity and scratch resistance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 3/28 C08K 3/28 5/09 5/09 C08L 101/14 C08L 101/14 C09D 7/12 C09D 7/12 129/04 129/04 185/00 185/00 201/00 201/00 (72) Inventor Masayoshi Gigayama 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka 72) Inventor Naoto Iimura 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-city, Fukuoka Prefecture Inside Totoki Equipment Co., Ltd. (72) Inventor Keiichiro Nori 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka Toko F-term (reference) in Equipment Co., Ltd. 2H AK01B AK01D AK01E AK21B AK21D AK21E AS00D AT00A BA03 BA04 BA05 BA07 BA10A BA10C BA10E BA13 DE01C GB07 JB05C JB20 JD15B JD15D JD15E JL07 JM02B JM02E JN01 YY00 YY00C 4G059 AA01 AC21 FA01 FA13 FA28 GA01 GA02 GA04 GA16 4J002 BE021 BG011 BQ001 DE136 DE146 DF028 DJ016 EF037 FD016 FD207 FD208 GA01 GC00 GG02 GH00 GL00 GN00 GP00 4J038 AA011 CE021 CG031 CK031 CL011 DF021 DM021 EA011 GA03 HA166 HA211 HA216 HA336 HA441 HA446 JA17 JA35 JA39 JC38 KA08 KA20 LA03 MA12 NA06 PB05

Claims (40)

[Claims] 1. A first coating comprising (a) a water-absorbing organic polymer, and a second coating comprising (b) a hydrophilic inorganic oxide and (c) a carboxylic acid-containing compound on the first coating. And a coating. 2. The method according to claim 1, wherein the first coating and the second coating are disposed between the first coating and the second coating.
The hydrophilic film according to claim 1, wherein a third coating is interposed, which comprises at least (a) a water-absorbing organic polymer, (b) a hydrophilic inorganic oxide, and (c) a carboxylic acid-containing compound. Sex material. 3. The hydrophilic material according to claim 1, wherein the first film and / or the third film further contains an inorganic binder. 4. The hydrophilic material according to claim 3, wherein the inorganic binder is a zirconium compound. 5. The hydrophilic material according to claim 4, wherein the zirconium compound is zirconium oxynitrate. 6. The hydrophilic material according to claim 1, wherein the water-absorbing organic polymer is polyvinyl alcohol. 7. The hydrophilic material according to claim 1, wherein the hydrophilic inorganic oxide is in the form of fine particles, and the mode of the particle diameter is 4 to 300 nm. 8. The hydrophilic material according to claim 1, wherein the hydrophilic inorganic oxide is silica and / or alumina. 9. The hydrophilic material according to claim 1, wherein the carboxylic acid-containing compound is citric acid and / or tartaric acid. 10. The first coating according to any one of 4 to 9, wherein the zirconium compound is present in a proportion of 50 to 150 parts by weight with respect to 100 parts by weight of the water-absorbing organic polymer. 3. The hydrophilic material according to 1. 11. The hydrophilic material according to claim 1, wherein the first coating further contains a hydroxyl group-containing organic compound. 12. The hydrophilic material according to claim 11, wherein the hydroxyl-containing organic compound is citric acid and / or tartaric acid. 13. The method according to claim 1, wherein the first coating and / or the third coating further comprises a first metal ion.
13. The hydrophilic material according to any one of 12 above. 14. The hydrophilic material according to claim 13, wherein the first metal ion is a monovalent metal ion. 15. The hydrophilic material according to claim 14, wherein the monovalent metal ion is a potassium ion. 16. The method according to claim 1, wherein the second coating and / or the third coating further comprises a second metal ion.
15. The hydrophilic material according to any one of the above items 15. 17. The hydrophilic material according to claim 16, wherein the second metal ion is a multivalent metal ion. 18. The hydrophilic material according to claim 17, wherein the multivalent metal ion is a magnesium ion and / or a calcium ion. 19. The method according to claim 1, wherein a contact angle of water on the surface of the hydrophilic material is 35 degrees or less.
The hydrophilic material according to any one of the above. 20. The method according to claim 1, wherein a contact angle of water on the surface of the hydrophilic material is 10 degrees or less.
The hydrophilic material according to any one of the above. 21. The hydrophilic material according to claim 1, wherein the hydrophilic material is an antifogging material. 22. The hydrophilic film according to claim 1, wherein a second film or a third film is formed on a surface of the first film opposite to the second film. Sex material. 23. A hydrophilic member, wherein the hydrophilic material according to claim 1 is applied to a surface of a substrate. 24. The hydrophilic member according to claim 23, wherein a first coating is formed on a surface of the substrate opposite to the first coating. 25. The method according to claim 23, wherein the substrate is transparent, and the obtained hydrophilic member is also transparent.
5. The hydrophilic member according to 4. 26. The hydrophilic member according to claim 23, wherein the hydrophilic member is an antifogging member. 27. The hydrophilic member according to claim 2, wherein the hydrophilic member is a high humidity zone hydrophilic member in a residential or non-residential facility.
The hydrophilic member according to any one of items 3 to 26. 28. The high humidity zone comprises a kitchen, a washroom,
The hydrophilic member according to claim 27, which is one of a bathroom and a toilet group. 29. A coating agent for forming the hydrophilic material according to any one of claims 1 to 22,
A hydrophilic coating agent set comprising: (a) a first coating agent containing at least a water-absorbing organic polymer; and (b) a second coating agent containing at least a hydrophilic inorganic oxide and (c) a carboxylic acid-containing compound. 30. The hydrophilic coating agent set according to claim 29, wherein the first coating agent further contains an inorganic binder. 31. The hydrophilic coating agent set according to claim 30, wherein the inorganic binder is zirconium oxynitrate. 32. The method according to claim 32, wherein the hydrophilic inorganic oxide is silica and / or
Or the hydrophilic coating agent set according to any one of claims 29 to 31, which is alumina. 33. The hydrophilic coating agent set according to claim 29, wherein the carboxylic acid-containing compound is citric acid and / or tartaric acid. 34. The pH of the first coating agent is 1.
The hydrophilic coating agent set according to any one of claims 29 to 33, wherein the number is 5 or more and 4 or less. 35. The pH of the first coating agent is set to 1.
35. The hydrophilic coating agent set according to claim 34, wherein an anion exchange resin is used when the number is 5 or more and 4 or less. 36. The first coating agent according to any one of claims 31 to 35, wherein the zirconium oxynitrate is present in a proportion of 50 to 150 parts by weight based on 100 parts by weight of the water-absorbing organic polymer. The hydrophilic coating agent set according to claim 1. 37. The method according to claim 29, wherein the first coating agent further comprises a hydroxyl group-containing organic compound.
36. The hydrophilic coating agent set according to any one of 36. 38. The hydrophilic coating agent set according to claim 37, wherein the hydroxyl group-containing organic compound is citric acid and / or tartaric acid. 39. The hydrophilic coating agent set according to any one of claims 29 to 38, wherein the first coating agent further contains a first metal ion. 40. The hydrophilic coating agent set according to any one of items 29 to 39, wherein the second coating agent further contains a second metal ion.