JP2002053792A - Water-absorbing coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite material having mar resistance, cleanability, anti-fogging performance, and good appearance and, simultaneously, each of anti-fogging performance to retard the time to fog the coated surface, stainproofness hard to be stained, and moisture condensation proofness free of drops of water. SOLUTION: A member which has high mar resistance and cleanability, and good alkali-resistant performance, acid resistance, anti-fogging performance, external appearance and the like can be produced by rendering the ratio of a zirconyl chelate in a zirconium compound or the composition ratio of zirconia to a vinyl alcohol-containing water absorbing organic polymer an optimum ratio.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-absorbing coating composition and a member mainly used around water.

[0002]

2. Description of the Related Art With regard to mirrors used in water-filled spaces, for example, mirrors placed in washrooms are often experienced that steam from hot water supply adheres to the surface and easily fogs, and loses the visibility of reflected images. It is. In order to solve this problem, a method has been considered in which a mirror surface is coated with a water-absorbing coating composition and a moisture-absorbing film is provided to exhibit anti-fog performance, as disclosed in JP-A-9-113704. Patents are currently being published. The term "hygroscopicity" or "hygroscopicity" as used herein means, for example, that even when condensed water or water droplets of hot water or moisture adhere to the mirror surface, they are absorbed by the coating composition and do not remain on the surface. By doing so,
It refers to a function of preventing the mirror surface from being clouded or overshadowed by moisture condensed water or water droplets. By the way, the above-mentioned patent discloses, for example, a coating composition containing polyacrylic acid, which is one of water-absorbing polymers, and a polymer having an OH group formed by hydrolysis and polycondensation of an inorganic alkoxide, each of which contains: And that it further contains a catalyst such as N, N-dimethylbenzylamine. The coating thus formed is a coating having not only moisture absorption performance but also water resistance that does not easily cause a problem that the coating melts or is easily peeled off even when the moisture absorbing coating is saturated with moisture.

[0003]

However, a mirror coated with such a hygroscopic coating composition causes a problem that the cleaning performance of the mirror surface is reduced. When the cleaning property is reduced, for example, when the mirror surface is fogged by being exposed to steam or the like, an act of wiping the surface with a cloth such as a towel is generally performed to remove the fogging.
Doing so with a coating of the coating composition can cause problems such as fibers of the towel remaining in the coating or the coating being damaged. This means that it is difficult to clean the mirror surface and the like with such a towel. Conversely, a surface that is easy to wipe with a towel or the like like an ordinary mirror without a coating is said to have high cleaning properties. Further, a coating composition obtained by using a polymer having an OH group formed by hydrolysis and polycondensation of the inorganic alkoxide as described above,
There is a tendency that air bubbles are easily trapped and a film containing bubbles is easily formed. Therefore, a method of mixing a zirconium salt aqueous solution such as zirconium nitrate or zirconium sulfate with a small problem of bubbles as it is with a water-absorbing polymer and using it as a water-absorbing coating composition is also conceivable. If the amount of added is increased to mix with the water-absorbing polymer, there arises a problem that the coating is colored, and it has not been put to practical use. In addition, a method of preparing a water-absorbing coating composition using zirconium oxychloride, which is relatively free from discoloration, is also conceivable, but this coating composition has a drawback of easily corroding the piping of a coating machine, and is not suitable for mass production. Not suitable.
In addition, as in patents such as U.S. Pat. No. 4,127,682, when zirconium nitrate is directly mixed with a water-absorbing polymer, the amount of zirconium nitrate is suppressed to a level that does not cause discoloration, and the shortage is reduced by a binder. An attempt was made to obtain a water-resistant anti-fog coating by supplementing with certain formaldehyde, but this method resulted in the extreme deprivation of the anti-fog performance of the water-absorbing polymer, resulting in insufficient anti-fog performance. There is a problem that only a coating can be obtained. In addition, these coatings have a pencil hardness of only about 2H, are highly likely to be damaged by human nails, and are not suitable as a moisture-absorbing anti-fog coating for mirrors requiring scratch resistance.

In the present invention, therefore, this moisture-absorbing film is provided with sufficient hygroscopicity and water resistance to provide cleaning properties, sufficient appearance and scratch resistance as a mirror or transparent material film, and Providing members with optimal anti-fog performance that has a sufficient length of anti-fog time until the surface becomes cloudy for the intended use, anti-fouling properties that do not easily get dirty, and dew-proofing properties that do not adhere to water drops The purpose is to:

[0005]

According to the first aspect of the present invention, there is provided a composition for absorbing a surface of a member to which the composition is applied, comprising a zirconium compound and a vinyl alcohol. Is the ratio of the molar concentration [a] / of the vinyl alcohol unit [b1] containing at least the (a) molar concentration [a] and the vinyl alcohol unit present in (b), containing at least the water-absorbing organic polymer and the solvent. [B1] is in the range of 0.2 to 0.4, and (a) the zirconium compound contains at least zirconyl chelate and / or ZrO ₂ . The (b) vinyl alcohol-containing water-absorbing organic polymer referred to herein is a polymer containing one or more vinyl alcohol units (see the following molecular formula) and obtained by copolymerization with another monomer such as vinyl acetate. Say Further, the molar concentration [a] of (a) referred to here is a molar concentration in the composition obtained by dividing the weight of the zirconium compound in the composition by the molecular weight of the zirconium compound. , (B) is defined as the molar concentration [b1] of the vinyl alcohol unit present in the composition obtained by dividing the weight of the vinyl alcohol alone in the composition by the molecular weight of the vinyl alcohol unit. It is a molarity. And this [a]
Divided by [b1] is [a] / [b1].

[0006]

Embedded image

In the present invention, a composition is obtained by combining a zirconium compound, the water-absorbing organic polymer, and a solvent, and [a] / [b1] is 0.2 to 0.2.
0.4, and (a) a zirconium compound containing at least zirconyl chelate and / or ZrO ₂ to obtain a coating obtained by coating the zirconium compound.
Compared with the composition obtained by setting [a] / [b1] to 0.2 or less, not only excellent results were obtained in terms of water resistance, cleaning properties, and scratch resistance, but also the inorganic alkoxide Compared to a composition having an OH group derived from a composition described in a patent such as Japanese Patent Application Laid-Open No. 9-113704 obtained by using a zirconium compound in place of a zirconium compound, it has a feature that the cleaning property is particularly improved. is there. Also, [a] / [b1] is 0.4
Compared with the composition obtained as described above, the film strength and the film discoloration are improved. Further, the coating composition is less likely to cause air bubbles to enter the coating agent, particularly as compared with a composition obtained by using the polymer having an OH group derived from the inorganic alkoxide instead of the zirconium compound. Therefore, there is also a feature that the appearance of a coating film obtained by coating the coating is less likely to be impaired.

According to a second aspect of the present invention, there is provided a composition for moistening a surface of a member to which the composition is applied, comprising a zirconium compound, a vinyl alcohol-containing water-absorbing organic polymer, , A solvent, and the ratio of [a] / [b1] is from 0.25 to 0.
32.

In the present invention, a coating composition is obtained by combining a zirconium compound, a vinyl alcohol-containing water-absorbing organic polymer, and a solvent.
[A] / [b1] is in the range of 0.25 to 0.32, and (a) the zirconium compound contains at least zirconyl chelate and / or ZrO ₂ , thereby coating it. The resulting coating may be a composition obtained by setting the ratio of [a] / [b1] to 0.25 or less, or 0.32 or more, or O derived from the inorganic alkoxide.
Compared to a composition obtained by using a polymer having an H group instead of a zirconium compound, not only good results in terms of water resistance and cleaning properties are obtained, but also film strength is considerably improved. Therefore, there is a feature that the scratch resistance is improved. In addition, compared to a coating composition obtained by a polymer having an OH group derived from the inorganic alkoxide, the composition is less likely to mix air bubbles into a coating agent, and in forming a film of the coating composition, There is a feature that the appearance of the coating is hardly impaired by bubbles.

According to a third aspect of the present invention, there is provided a composition according to the first or second aspect, wherein the solvent is a water-containing organic solvent. In the present invention, by the fact that the solvent is a water-containing organic solvent, compared to the case of water or only an organic solvent,
There is little change in viscosity, and a coating liquid with less air bubbles can be formed. Therefore, when the composition is coated on a member, adverse effects on the appearance such as air bubbles entering the film are less likely to occur, and this is particularly effective in maintaining a good appearance. This effect is remarkable when coating is performed by feeding the coating liquid into a mass-production coating machine such as a curtain coater.

According to a fourth aspect of the present invention, there is provided the invention, wherein the zirconyl chelate is zirconyl oxynitrate. In the present invention, since the zirconyl chelate is zirconyl oxynitrate, compared to zirconium oxychloride, there is no problem such as corrosion of the metal, and the influence on the piping of the coating machine is small, so that the durability of the mass production machine is improved. The effect is obtained.

[0012] In order to solve the above-mentioned problem, the invention according to claim 5 is characterized in that the vinyl alcohol-containing water-absorbing organic polymer contains at least polyvinyl alcohol. In the present invention, the use of polyvinyl alcohol as the vinyl alcohol-containing water-absorbing organic polymer has an effect of particularly high water resistance as compared with polyacrylic acid, which is another water-absorbing organic polymer. The term "water resistance" as used herein refers to the performance of a coating such that a liquid such as water comes into contact with a moisture-absorbing coating and the strength of the coating does not decrease even when absorbed by the coating. For example, when a mirror coated with polyvinyl alcohol is held in water for 1 minute or more, and after it is taken out of 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 the surface of the film 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. Furthermore, there is a high effect in terms of cleanability.

[0013] In order to solve the above-mentioned problems, the invention according to claim 6 is characterized in that the degree of saponification of polyvinyl alcohol is 98% or more. In the present invention, by setting the saponification degree of polyvinyl alcohol to 98% or more, even when a material such as zirconium oxynitrate or zirconium oxysulfate which easily causes discoloration of the film is used as the zirconium chelate, the saponification degree is 9%.
Compared to the case where polyvinyl alcohol such as 0% is used, there is an effect that discoloration of the film is less likely to occur and the transparency of the film is not impaired.

According to a seventh aspect of the present invention, a solution is provided, wherein the composition has a pH of 2.5 or more. In the present invention, the p
By making H 2.5 or more, the discoloration of the resulting film is less likely to occur, and the effect of less impairing the transparency of the film and the effect of improving the film strength are obtained as compared with other cases. Can be This effect is remarkable in a material such as zirconium oxynitrate or zirconium oxysulfate, which easily discolors the coating.

[0015] In order to solve the above-mentioned problem, the invention according to claim 8 is characterized in that the ZrO ₂ is produced from a zirconyl chelate. In the present invention, the Zr
By generating O ₂ from a zirconyl chelate, the viscosity of the composition can be adjusted to a viscosity suitable for storage or mass-production coating. As a method for preparing the above-mentioned ZrO ₂ , a method obtained from an aqueous solution is suitable, and the main method is a method obtained by hydrolysis of zirconyl chelate and zirconium alkoxide. The latter of the two has the disadvantage that during the hydrolysis, the polymerization reaction also proceeds at the same time, so that it is easily aggregated and difficult to handle. Therefore, the former obtained by hydrolysis of the zirconyl chelate is easy to handle, and there is an advantage that a transparent solution free from aggregation is obtained even when the composition is prepared using this. Further, as a method of hydrolyzing the zirconyl chelate, there are various methods such as heating, pressurization, and addition of a catalyst, all of which are suitably used, but in the composition, the aqueous solution of the aqueous solution at a temperature around 100 ° C. Heat treatment is the most preferable method. This method is particularly effective when zirconium oxynitrate or zirconium oxysulfate is used. This is because, even when the pH of the composition is adjusted to a pH such as pH 2.5, at which the discoloration of the coating is unlikely to occur, the viscosity of the liquid is not drastically increased as compared with the case without heat treatment or other methods. This is because the rise can be reduced. Incidentally, as can be seen from the fact that the discoloration of the film becomes more remarkable as the pH of the zirconium or ZrO ₂ solution is lower, it is considered that the discoloration is caused by oxidation of vinyl alcohol by nitric acid. Therefore, it is considered that discoloration of the coating film is reduced by removing nitric acid or nitrate ion, which is the cause thereof. Therefore, in order to remove this nitrate ion, a method of removing it with an anion-sympathetic resin or the like is conceivable.However, if too much removal is performed and the pH of the aqueous solution is increased, a sharp increase in viscosity is caused. Become. However, when the composition is heated and then removed, even if the pH of the composition is adjusted to pH 4, the rapid increase in viscosity of the composition is reduced, so that there is an effect that the composition can be maintained at a stable liquid viscosity. In addition, since the viscosity of the liquid varies depending on the heating time and the heating temperature, the viscosity can be easily controlled by controlling the conditions well. Thus, the method of producing ZrO ₂ by heat treatment of zirconyl chelate is an effective method for controlling the viscosity of the liquid of the composition.

According to a ninth aspect of the present invention, there is provided a method for producing ZrO ₂ from a zirconyl chelate, which further comprises a catalyst. In the present invention, when ZrO ₂ is produced from a zirconyl chelate, by further including a catalyst, the effect of improving the antifogging performance without lowering the former cleanability can be obtained.

In the invention according to claim 10 which has been made to solve the above-mentioned problem, the catalyst comprises ammonia and / or ammonia.
Alternatively, it is characterized by being hydrogen peroxide. In the present invention, when ammonia and / or hydrogen peroxide is used as a catalyst, a film which can maintain a considerably high hygroscopic property without lowering the cleaning property as compared with other catalysts can be obtained.

[0018] In the invention according to the eleventh aspect of the present invention, when the ZrO ₂ is produced from a zirconyl chelate, the zirconyl chelate further includes an yttrium salt and / or a magnesium salt. It is characterized by. In the present invention, when the ZrO ₂ is generated from a zirconyl chelate, the zirconyl chelate further includes an yttrium salt and / or a magnesium salt, thereby reducing the film strength as compared with the case where the zirconyl chelate is not included. The thickness can be increased. Therefore, there is an effect of improving the anti-fog performance without reducing the film strength.

According to a twelfth aspect of the present invention for solving the above-mentioned problems, zirconium oxyacetate is further included. In the present invention, the composition further contains zirconium oxyacetate so that the viscosity of the coating liquid as the composition is 0.1 Pa ·
It has the effect of maintaining a low viscosity of around s and stabilizing the liquid. Depending on the composition of the coating liquid, the viscosity may increase significantly in a short time, and may increase to a viscosity of 1 Pa · s or more after being left for one hour after the preparation of the liquid, so that the base material may not be coated. Zirconium oxyacetate is effective in preventing such a problem.

According to a thirteenth aspect of the present invention, when the ZrO ₂ is produced from a zirconyl chelate, the zirconyl chelate further comprises zirconium oxyacetate. .
In the present invention, when the ZrO ₂ is generated from a zirconyl chelate, the zirconyl chelate further includes zirconium oxyacetate to generate a coating solution having a viscosity of about 0.1 Pas. It has the effect of keeping the viscosity low and stabilizing the liquid. The addition of zirconium oxyacetate as described in the twelfth aspect is effective in lowering the viscosity and stabilizing it, but there is a disadvantage in that if it is added too much, air bubbles are easily involved in the solution of the composition. Therefore, there is a limit to the addition of the zirconium oxyacetate. However, when zirconium oxyacetate is added and used by the above-described method, the viscosity of the solution can be stabilized without involving air bubbles in the solution.

In the invention according to claim 14 which has been made to solve the above-mentioned problem, the composition has an average particle diameter of 0.5
It is characterized by having ZrO ₂ of ４０40 nm. In the present invention, ZrO ₂ having an average particle size of 0.5 to 40 nm is added to the composition.
With this, it is possible to improve the transparency of the coating film obtained from the composition and to prevent the coating from becoming cloudy. This thing More particularly, when using the average particle diameter 40nm or more ZrO _2, a phenomenon that the film becomes clouded is observed, when using less ZrO _2, such a problem does not occur. At the same time, 0.5
ZrO ₂ having an average particle diameter of not less than nm has an aspect that the viscosity of the composition is less sharply increased than that of ZrO ₂ having a mean particle diameter of less than that and is easy to handle.

According to a fifteenth aspect of the present invention, a fine inorganic oxide is mixed with the composition. The term “particulate inorganic oxide” as used herein refers to an inorganic oxide such as particulate silica, alumina, titania, and zirconia, preferably having an average particle diameter in the range of 5 nm to 200 nm. Examples include silica sol. In the present invention, when the particulate inorganic oxide is mixed into the composition, the value of the composition ratio of the zirconium compound in the composition, [a] / [b1], can be reduced, and particularly, zirconium oxynitrate When zirconium oxysulfate is used, discoloration of the coating can be reduced. Also, the phenomenon of a decrease in the water resistance or the like of the coating film caused by the inorganic oxide can be prevented by using the inorganic oxide as a binder, which does not cause discoloration. From these facts, by using this method, it is possible to obtain a film with less discoloration while maintaining good scratch resistance, that is, good film strength and cleanability.

[0023] In the invention according to claim 16 which has been made to solve the above-mentioned problem, the composition has a thickness of 5 nm to 200 n.
It is characterized in that particulate silica having an average particle diameter in the range of m is mixed. In the present invention, 5
Incorporation of particulate silica having an average particle size in the range of nm to 200 nm is more difficult when using zirconium oxynitrate or zirconium oxysulfate than when using other particulate inorganic oxides such as alumina sol. A film with little discoloration can be obtained while maintaining good scratch resistance and cleanability.

[0024] The invention according to claim 17 for solving the above-mentioned problem is characterized in that formaldehyde is further mixed into the composition. In the present invention, by further mixing formaldehyde into the composition, a coating film having improved alkali resistance can be obtained as compared with the case where the above-mentioned composition is not used.

[0025] In order to solve the above-mentioned problem, the invention according to claim 18 is characterized in that the surface of a member to which the composition is applied is provided with antifogging property. For example, in the case of a mirror, when small water droplets such as steam adhere to the mirror surface, irregularities due to the water droplets are generated on the mirror surface, irregularly reflect the light to be inserted, and reflected on the mirror The result is that the visibility of the reflection image is lost, but by applying the composition to the surface of the member, it means that the mirror surface can be prevented from fogging and the visibility of the reflection image can be maintained.

In the invention according to claim 19, which has been made to solve the above-mentioned problem, on the surface of a member to which the composition is applied, condensed water of moisture adhering to the surface and / or
Alternatively, water droplets can be absorbed by the surface of the coating, whereby the coating prevents the surface from being clouded or overshadowed by condensed water and / or water droplets of moisture. In the present invention, for example, by coating a base material surface such as a mirror with the composition, when minute moisture such as steam comes into contact with the film surface of the mirror, condensed water and / or water droplets of the moisture are formed. Without dew condensation on the film surface, it reaches and is absorbed by the water-absorbing organic polymer in the water-absorbing coating composition forming the surface layer, so that it is possible to prevent fogging or shadowing and maintain the visibility of the reflected image .

In the invention according to claim 20 which has been made to solve the above-mentioned problem, the surface of a member to which the composition has been applied is provided with dew-proofing properties on the surface of the member to which the composition has been applied. It is characterized by the following. Here, the term "dew-proofing property" means that the surface layer of the substrate has a function of preventing the following phenomena. The phenomenon is that when small water droplets such as steam come into contact with the surface of the member, it is rapidly cooled due to the difference in temperature between the air and the surface layer, and the water droplets are condensed, and the size can be visually determined. This is a phenomenon that water droplets are formed and adhere to the substrate surface layer. In the present invention, by coating the surface of the base material with the composition, it is possible to provide the above-described anti-dew property. The reason for this is that, for example, by coating a base material surface such as a mirror with the above composition, when minute moisture such as steam comes into contact with the mirror film surface, condensed water and / or water droplets of the moisture are formed. This is because the water reaches the water-absorbing organic polymer in the water-absorbing coating composition forming the surface layer without being condensed on the film surface and is absorbed.

Claims made to solve the above problems
21. The method for preparing a composition according to any one of claims 1 to 20, wherein the (a) zirconium compound is added to the (c) solvent when mixing the composition. The method is characterized in that after the solution is diluted and the pH of the solution is adjusted to 2.5 or more, the ZrO ₂ is formed or mixed with the above (b). In the present invention, when the composition is mixed, the (a) zirconium compound is mixed with the (c)
After diluting in a solvent and adjusting the pH of the solution to 2.5 or more,
By forming the ZrO ₂ or by mixing it with the above (b), it is possible to not only prevent discoloration of the coating, but also to prepare a coating having high coating strength.

Claims made to solve the above problems
22. The invention according to item 22 is a method for hygroscopicizing the surface of a member, the method comprising applying the composition to the surface of the member, and drying or curing the composition. In the present invention, by using the method as described above,
For example, a member such as glass or plastic can be easily coated with the water-absorbing coating composition. 24. A solution for solving the problem.
The described invention is characterized in that before applying the composition according to any one of claims 1 to 21 to the surface of a member, the surface of the member is washed with a cleaning agent in advance. In the present invention, by using the method as described above, for example, when coating the water-absorbing coating composition on a member such as glass or plastic,
For example, there is no problem that bubbles enter the solution, and the solution can be coated with almost the same appearance as the member. This means that cleaning with a cleaning agent not only removes impurities on the member surface, but also depends on the method.
This is because the surface of the member can be smoothed by polishing, the contact angle of the contacting liquid can be reduced, and the member can be made hydrophilic, so that air bubbles do not bite during coating.

[0030] The invention according to claim 24 made to solve the above-mentioned problem is characterized in that the cleaning agent is a ceria-containing liquid. In the present invention, the cleaning agent,
By being a ceria-containing liquid, when washing a member with a liquid containing ceria, there is an effect of polishing the member, and by using a neutral detergent or the like as a liquid for mixing the member, the surface of the base material can be washed. Impurities such as fats and oils can be removed. Therefore, the cleaned member becomes a clean hydrophilic member surface, has good wettability, and is easily coated with the water-absorbing coating composition. In addition, the adhesion between the member and the coating is improved.

The invention according to claim 25, which has been made to solve the above-mentioned problem, is characterized in that before applying the composition to the surface of a member, the surface of the member is made hydrophilic in advance. . In the present invention, when the surface of the member is preliminarily etched and hydrophilized with an aqueous solution of sodium hydroxide or the like, when the member is coated with the water-absorbing coating composition, for example, there is a problem that bubbles enter the solution. The present invention provides a method for forming a coating film having good adhesion to a member, which can be coated in a state where the appearance is almost the same as that of the member without generation of a member.

[0032] The invention according to claim 26, which has been made to solve the above problem, is characterized in that the hydrophilization is a corona discharge surface treatment. In the present invention, by performing a corona discharge surface treatment as the hydrophilization, the hydrophilicity of the member becomes higher than that of a hydrophilization method such as etching, and a clean film can be formed, and a film having high adhesion can be obtained. There are features. In addition, the effect is further improved by using the cleaning with ceria polishing together.

The invention according to claim 27, which has been made to solve the above problem, is a method for manufacturing the member, wherein the member is transparent, and the obtained hygroscopic surface is also transparent. I do. In the present invention, the member is transparent, the resulting hygroscopic surface is also transparent, for example, not only does not have a problem in appearance in the coating on a member that values transparency, such as coating on glass, , And other types of members such as plastic.

According to a twenty-eighth aspect of the present invention, there is provided a method of applying the composition to a member surface when applying the composition to a member surface and drying or curing the composition. It is characterized by curtain coating. In the present invention, by performing curtain coating as a method of applying the composition to the member surface, for example, in coating the composition on a large mirror having a size of 1 square meter, a large amount of coating can be applied in a short time. It becomes possible. Curtain coating here means that the coating liquid is stored in a storage tank, circulated in a pipe with a pump, and the coating liquid is dropped from a long slit-like hole like a curtain-shaped waterfall, In addition, the mirror which is the base material, using a special conveyor,
This is a technique in which coating is performed by passing the coating liquid on the base material in a certain fixed amount at a certain fixed speed.

According to a twenty-ninth aspect of the present invention, there is provided a method of applying the composition to a member surface and drying or curing the composition by a one-coat two-bake method. It is characterized by comprising. In the present invention, by performing the one-coat two-bake method, a film having both antifogging property and film strength can be obtained without discoloration of the film.

The invention according to claim 30, which has been made to solve the above problem, is to apply the composition to the surface of a member and, when drying or curing the composition, use a heat source to apply the composition to the member. Characterized in that it is placed on the back side of the surface. In the present invention, by disposing the heat source on the back surface side of the member surface to which the composition is applied, the coating does not discolor and the anti-fogging process is performed as compared with the case where the heat source is disposed on the member surface to which the composition is applied. The characteristic feature is that a film having both properties and film strength can be obtained in a short time. The heat source referred to here is a device serving as a source for irradiating heat for heating, and in the case of a device for electrically heating, for example, a heating portion of an electric heater,
Refers to the lamp part of the near infrared lamp. In the case of a device that generates heat by gas, it refers to, for example, a burner portion of a gas burner.

According to a thirty-first aspect of the present invention, the heat source is a far-infrared lamp. In the present invention, by making the heat source a near-infrared lamp, compared to an electric heater,
A film having both antifogging property and film strength can be obtained in a short time without discoloration of the film.

The invention according to claim 32, which has been made to solve the above problem, is to apply the composition to the surface of a member, and to dry or cure the composition, after drying or curing the composition, Characterized by comprising a step of inundating the water. In the present invention, a film having improved antifogging properties can be obtained by including the step of immersing the composition in water.

[0039] The invention according to claim 33, which has been made to solve the above-mentioned problem, is characterized in that the immersion is steam cleaning. In the present invention, since the immersion is steam cleaning, a film having improved antifogging properties can be obtained in a shorter time than a method of immersing a member coated with the composition in a water tank. The term “steam cleaning” here refers to the generation of 1
This device saturates the moisture-absorbing film with water by applying steam near 00 ° C uniformly to the film. In this case, it is effective to apply water having a low temperature to some extent.

The invention according to claim 34, which has been made to solve the above problem, is characterized in that it is a member having a surface that has been made hygroscopic and obtained by the manufacturing method. In the present invention, the member having the above-described anti-fogging property, dew-proofing property, and the like can be provided by the member having a surface that has been made hygroscopic by the manufacturing method.

The invention according to claim 35, which has been made to solve the above-mentioned problem, is characterized in that the member is a mirror. In the present invention, since the member is a mirror, it is possible to provide a mirror having the above-described anti-fogging property, dew-proofing property and the like.

According to a thirty-sixth aspect of the present invention, the member is a transparent plate-like member. In the present invention, since the member is a transparent plate member, it is possible to provide a transparent plate member having the above-described anti-fogging property, dew-proofing property, and the like.

According to a thirty-seventh aspect of the present invention, there is provided a liquid crystal display device, wherein the member is a transparent lens. In the present invention, since the member is a transparent lens, it is possible to provide a transparent lens having the above-described anti-fogging property, dew-proofing property and the like.

According to a thirty-eighth aspect of the present invention, there is provided a liquid crystal display device, wherein the member is a transparent film. In the present invention, when the member is a transparent film, it is possible to provide a transparent film having the above-described anti-fogging property, dew-proofing property and the like.

[0045]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The water-absorbing coating composition of the present invention
The product is a zirconium compound and vinyl alcohol-containing water
Characterized by containing a conductive organic polymer and a solvent
Water-absorbing coating composition. Generally known
Zirconium compounds include Zr whose oxidation number is difficult to identify.
H_Two, ZrB, ZrC, ZrSi_Two, ZrN, ZrP, Z
rS_Two[Zr ｛P (C) having an oxidation number of 0
H_Three)_Three｝ (Η⁶-toluene)_Two], [Zr (C₀)_Two(Η ^Two-
C_FiveH₆2), ZrCl having an oxidation number of 1 and ZrCl having an oxidation number of 2
X_Two(X = Cl, Br, I), ZrX having an oxidation number of 3_Three(X
= Zirconium having an oxidation number of 4, such as F, Cl, Br, I)
The compound zircon ZrSiO_FourOr halogenated sill
ZrX which is conium_Four(X = F, Cl, Br, I),
ZrO_TwoZirconia, ZrOm (OH) n (m = 4-
n, an integer of 4 ≧ n ≧ 0) zirconium oxoate, M4Z
rO_Four, M_TwoZrO_Three(M = Na, K, 1 / 2Ca, 1 / 2Pb)
Zirconate, zirconium nitrate, zirconium sulfate
Zirconium hydroxide, [ZrF₆]^2-, [ZrF₈]
^Four-Fluoro complexes of zirconium fluoride such as
+2 valent represented by ZrO called zirconyl chelate
Group of zirconium oxychloride, hydroxylated oxychloride
Zirconium, zirconium oxyhydroxide, oxynitric acid
Zirconium, zirconium oxyacetate, dioxysulfate
Ruconium, zirconium oxycarbonate, oxystearyl
Zirconium phosphate, zirconium oxyoctylate,
In addition, a polymer was obtained by hydrolysis / polycondensation reaction.
Zr (OCH_Three)_FourZirconium alkoxy like
And others. Further, as the zirconium compound,
There are oxides, oxyacid salts, organic acid salts or complex salts.
And at least one of those which are stable in the processing solution
Can be used in combination with zirconium compounds
Noh. Specifically, ZrO _Two, ZrO_Two・ XH_TwoO,
M_TwoZrO_Three(Zirconic acid and acid salt), M is alkali
Metal, ZrO_Three・ 2H_TwoO, K_FourZrO_Four・ 2H_TwoO_Two・ 2H
_TwoOxides such as O (peroxozirconate) and
A related compound of ZrO (H_TwoPO_Four)_Two, ZrP_TwoO ₇, Z
Oxygenates such as rSiO4, zirconium hydroxychloride
Such as zirconium halide, zirconium formate, acetic acid
Zirconium, zirconium propionate, caprylic acid
Organic acids such as zirconium and zirconium stearate
Ruconium salt, ammonium zirconium carbonate, di sulfate
Sodium ruconium, ammonium zirconium acetate
System, sodium zirconium oxalate, zirconium citrate
Sodium, zirconium ammonium citrate
And zirconium complex salts.

The zirconium compound, especially the oxide, is a compound which is said to have particularly good acid resistance, water resistance and alkali resistance among other inorganic compounds such as silicon, titanium and aluminum. Among them, zirconyl chelates and zirconium alkoxides are liable to undergo hydrolysis and polycondensation reactions, and are useful materials both as binders and as starting materials for ZrO ₂ . However, the hydrolysis / polycondensation reaction from an alkoxide is considerably faster than other ones, and phenomena such as aggregation in a solvent are liable to occur. Therefore, zirconyl chelates are useful in terms of ease of handling.

The zirconium compound used in the present invention contains at least one of zirconyl chelate and ZrO _{2 in} the zirconium compound, and may contain any of the zirconium compounds. Examples of the ZrO ₂ include those obtained by subjecting zircon ZrSiO ₄ or baddeleyite to heat treatment or chemical treatment and then separating silica, and those obtained by hydrolysis of zirconyl chelate or zirconium alkoxide. I do. Unlike the former, the latter can be handled as an aqueous solution, so that when the above composition is prepared, it is a convenient material in that a transparent solution can be prepared. For these reasons, zirconyl chelate and zirconyl chelate-derived ZrO ₂ are preferably used for the reasons described above.

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 chlorine ions with water molecules. 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, the OH group of the vinyl alcohol-containing water-absorbing organic polymer present in the composition reacts with the hydrolyzed zirconium compound or the polymer having an OH group to form an inorganic portion of Zr and an organic compound derived from the water-absorbing organic polymer. A composite polymer having a moiety is formed. When the components of the composition are mixed, the hydrolysis reaction and the polycondensation reaction partially proceed as described above, and thus the polycondensation of the hydrolyzate such as a zirconium compound, a hydrolyzate thereof, and zirconia is performed. A polymer, a vinyl alcohol-containing water-absorbing organic polymer, and a polycondensation or cross-linking reaction product of a hydrolyzate derived from the zirconium compound and a water-absorbing organic polymer are mixed to form a colloidal sol. This becomes the water-absorbing coating composition. At this time, an inorganic compound such as titania or silica or an organic compound may be mixed as other compounds.

Zirconium nitrate is expressed as Zr (NO ₃ ) ₄ , but in dry air, it releases nitric acid at _first and changes to zirconium oxynitrate ZrO (NO ₃ ) ₂ . Therefore, ordinary commercial products exist in this state.
By the way, this reagent, like other zirconyl chelates such as zirconium oxychloride, crosslinks with a vinyl alcohol-containing water-absorbing organic polymer to form an inorganic part of Zr,
A composite polymer having an organic moiety derived from a water-absorbing organic polymer can be formed. However, when a film is formed by applying it to a member, unlike zirconium oxychloride, there is a drawback that the film turns yellow-brown depending on the heating method. On the other hand, unlike zirconium oxychloride, there is no problem 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 the overall point of view, it can be seen that zirconium oxynitrate is a preferable material for forming the most hygroscopic or water-absorbing coating among zirconium compounds.

The biggest problem of the zirconium oxynitrate, namely, the discoloration of the coating to yellow-brown, is that nitric acid obtained from nitrate ions present in zirconium oxynitrate reacts with OH groups of vinyl alcohol. Seems to be the cause. Therefore, it is first necessary to remove the nitric acid or nitrate ions in order to prevent discoloration.

Incidentally, the discoloration of the coating film referred to herein is caused by a heating and drying process after the composition is applied to a member, and the heating conditions under which the discoloration occurs include the application amount of the composition, the heating temperature, It tends to be different depending on the heating time.
For example, when a film having a thickness of 8 μm is to be formed from a composition having a certain composition, even if the film is discolored when heated in an atmosphere at 150 ° C. for 20 minutes, the film may be discolored by 1%.
Discoloration may not occur when heated under slightly reduced conditions.
However, the latter coating is an uncured coating,
Water resistance and scratch resistance tend to decrease in many cases. Thus, when the coating is completely cured, the water resistance and scratch resistance are good, but the discoloration is apt to occur. . Therefore, by finding the optimal conditions of heating and drying that do not cause discoloration when the coating is completely cured, a coating without discoloration can be obtained. Therefore, the problem of discoloration of the coating can be solved by minimizing the content of nitrate ions in the composition and finding the optimal conditions for heating and drying.

There are various methods for minimizing the nitrate ion, but 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 composition from which the film is formed sharply increases,
If done too much, it will change to 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 concentration of 8 to 10%, the pH is controlled to be in the range of 2.0 to 4. The removal of nitrate ions by an anion exchange resin is preferred, and the pH is more preferably 2.5 to 3. When the pH is lower than the above, the discoloration of the coating is remarkable.
With the above values, the viscosity of the composition increases sharply.

By the way, in the film obtained by the above method, the discoloration of the film is considerably reduced, but it is not completely suppressed. It is necessary to further suppress the discoloration of the film by removing nitrate ions. For this purpose, it is necessary to release nitrate ions from zirconium oxynitrate in the solution as much as possible, and to remove the released parts in some form. As a method for releasing nitrate ions from the zirconium oxynitrate as much as possible in the solution, pressurize or heat this aqueous solution, or add a catalyst such as ammonia or hydrogen peroxide to release it at room temperature. A method is conceivable. When the releasable portion of the nitrate ion is released as much as possible by one of the heating methods, 95% of the aqueous solution of zirconium oxynitrate is used.
Heating at a high temperature such as ° C. is carried out to carry out a reaction to generate zirconium hydroxide or oxide, to release nitrate ions generated in the reaction, and then remove the ions with an anion exchange resin. (Hereinafter, the solution obtained at this time is called a heated zirconia solution.) As a method at this time, an anion exchange resin is mixed in advance with an aqueous solution of zirconium oxynitrate until the pH of the solution becomes 2-3. In some cases, heating is performed after stirring, and in other cases, heating is performed without such pH adjustment from the beginning. But there's nothing particularly good.

As a general operation of this heating method, a zirconium oxynitrate solution is usually put into a mayonnaise bottle with a lid together with a stirrer, and stirred at 100 ° C.
React for a certain period of time at a close temperature. It is preferable to perform the stirring at this time as much as possible, even if the heating operation is performed under the same conditions, in order to prevent a problem that the liquid property such as the pH and the particle size distribution of zirconia changes each time the operation is performed. The heating temperature is 100 ° C. since the reaction solution is an aqueous solution.
The temperature is preferably 50 ° C. or higher, and 100 ° C. or lower 90 ° C.
The temperature close to the boiling point of water is more preferable, and
If it is lower than that, it may take time to prepare a liquid having a target liquid property. Further, the heating time is a factor to be strictly adjusted when preparing the water-absorbing coating composition, because the liquid properties such as the pH of the heated zirconia solution and the particle size distribution of zirconia may vary depending on the heating time. For example, in the case of a solution in which an aqueous solution of zirconium oxynitrate having a solid concentration of 9% is adjusted to pH 3 with an anion exchange resin in advance, when the heating time is 2 to 18 hours, the particle size of zirconia generated is 1 to 5 nm. However, when the time exceeds 18 hours, the particle size grows rapidly and becomes fine particles of 40 nm or more. When the above-mentioned fine particles are used to form the hygroscopic film, the film becomes cloudy and the transparency is impaired. When the heating time is out of the range of 4 hours to 10 hours, the viscosity of the composition produced thereby tends to increase. For these reasons, the heating time is preferably in the range of 4 hours to 10 hours. Particularly, the range of 5 to 8 hours is preferable. In addition, the standing time of the liquid after heating until the next operation is performed is preferably as long as possible, and is preferably one week or more, preferably one month or more. However, there is no particular problem as long as the viscosity is adjusted well even for a standing time of about one day.

As described above, when the aqueous solution of zirconium oxynitrate is once heated and then the nitrate ions are removed, the pH of the composition becomes higher than that of the case without heating.
Even when the composition becomes, the rapid increase in viscosity of the composition is reduced, so that it is possible to maintain a stable liquid viscosity and to prevent discoloration of the coating. As a reason for this, when nitrate ions are removed without heat treatment, the reaction between the zirconium compound as a binder and the vinyl alcohol-containing water-absorbing polymer progresses quite rapidly, so that the two are not uniformly mixed and uneven. In other words, the two do not disperse in water, but combine locally in a hardened state, whereby the water solvent that plays a role in suppressing the polymerization reaction due to dehydration condensation like this time has separated from both. It is considered that the reaction proceeds in a state, and the polymerization reaction rapidly proceeds. On the other hand, when nitrate ions are removed after the heat treatment of the aqueous solution of zirconium oxynitrate, the zirconium compound changes to some extent from the zirconium compound to zirconia in advance by the heat treatment, and reacts with the vinyl alcohol-containing water-absorbing polymer in the changed state. Therefore, the amount of hydroxide ion, which is a portion responsible for bonding the zirconium compound to the polymer, is relatively small, and the reaction proceeds slowly. Therefore, it is considered that both are easily dispersed, and both react in a uniform state, so that a rapid change in viscosity of the composition is reduced.

For example, the above-mentioned zirconyl chelate having a solid content of 9% usually has a pH of 1.5 or less. However, even if a coating solution is prepared by using the zirconyl chelate as it is, discoloration of the coating occurs, and the coating strength decreases. Often, only low coatings are obtained. However, if the pH is readjusted to 2.5, there is less fear of discoloration of the coating, and a coating having high coating strength can be obtained. However, such a liquid also has a disadvantage that the viscosity increases immediately and solidifies in a short time. Therefore, the solution is heated for 5 hours in an atmosphere of 95 ° C. from the state of pH3, and then the pH is adjusted again to prepare a coating solution. Almost no liquid can be prepared.

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. Regarding the method of ion exchange, there are various methods such as putting a zirconium oxynitrate solution in a reaction tank, filling an anion exchange resin in a cylindrical column, and flowing the liquid in the reaction to react. Although it can be taken, the method is not particularly limited. The shape of the obtained ZrO ₂ may be any of a granular shape and a chain shape, and is not particularly limited.

Further, at the time of this heating, a catalyst may be added. Such catalysts include hydrolysis catalysts such as hydrochloric acid and acetic acid for imparting hydroxide ions to zirconium compounds or zirconyl chelates to form zirconyl hydroxide, and dehydration polymerization such as converting zirconyl hydroxide to ZrO _2. There is a curing catalyst such as ammonia or hydrogen peroxide that promotes.

Further, by adding a yttrium salt or a magnesium salt capable of increasing the strength of the generated ZrO ₂ itself and then performing a heating operation, the film strength can be improved. The amount of this reagent used is preferably 5 to 80 parts by weight, more preferably 30 to 60 parts by weight, based on 100 parts by weight of the zirconium compound. As the yttrium salt, yttrium chloride, yttrium nitrate, yttrium sulfate, yttrium acetate, yttrium carbonate and other yttrium salts can be suitably used,
Others can also be used. Further, as the magnesium salt, magnesium salts such as magnesium chloride, magnesium nitrate, magnesium sulfate, magnesium acetate, magnesium carbonate and the like can be suitably used, and other magnesium salts can also be used.

Further, by adding zirconium oxyacetate capable of suppressing the reaction speed of the dehydration condensation reaction from zirconyl chelate to ZrO ₂ in advance and then performing a heating operation, a rapid increase in the viscosity of the composition can be suppressed. Can do things. The amount of this reagent to be used is preferably 5 to 15 parts by weight, more preferably about 8 parts by weight, based on 100 parts by weight of the zirconium compound. This zirconium oxyacetate can exert the same effect even when added directly to the composition. However, if it is added too much, it becomes easy for bubbles to be entangled in the composition, which may impair the appearance of the coating. Therefore, the addition amount of this zirconium oxyacetate is 1 to 100 parts by weight of the composition.
It is preferable to add 10 parts by weight, more preferably 4 parts by weight.
８8 parts by weight.

The present invention provides a zirconium compound,
Is a zirconyl chelate. That zirconium
Zirconyl compounds such as those in the above reagents
Zirconium oxynitrate, one of the rates
Zirconium chloride, zirconium oxyacetate, oxysulfur
One of zirconium nitrate in addition to zirconium oxide
Zr (OH)_Two(NO_Three)_Two・ 4H_TwoO, ZrO (N
O_Three)_Two, Zr_TwoO_Three(NO_Three)_Two, Zr_FourO₇(NO_Three)_TwoEtc.,
Zirconium acetate, zirconium fluoride, bromide
Zirconium, zirconium iodide, oxyhydroxide
Zirconium, zirconyl carbonate (zirconium oxycarbonate
Um), zirconyl hydroxide, zirconyl acetate, carbonic acid
Zirconyl ammonium, zircony stearate
And zirconyl octylate are used. In addition,
Ruconium compounds include oxides, oxyacid salts, organic acids
There are salts or complex salts, which are aqueous and stable in the processing solution
In combination with at least one zirconium compound such as zirconyl.
It is also possible to use them together. Specifically, Z
rO _Two, ZrO_Two・ XH_TwoO, M_TwoZrO_Three(zirconium
Acid and acid salt), M is an alkali metal, ZrO_Three・ 2H_TwoO,
K_FourZrO_Four・ 2H_TwoO_Two・ 2H_TwoO (periox zirconi
Oxides and related compounds such as ZrO (H
_TwoPO_Four)_Two, ZrP_TwoO ₇Oxyacids, such as ZrSiO4,
Zirconium halides such as zirconium hydroxychloride
, Zirconium formate, zirconium acetate, propion
Zirconium, zirconium caprylate, stearin
Organic acid zirconium salts such as zirconium acid, zirconate carbonate
Ammonium ammonium, sodium zirconium sulfate, vinegar
Ammonium zirconate, zirconium oxalate
Thorium, sodium zirconium citrate, citric acid
Zirconium complex salts such as zirconium ammonium
I can do it.

As the vinyl alcohol-containing water-absorbing organic polymer used in the present invention, polyvinyl alcohol can be suitably used. The term “polyvinyl alcohol” as used herein means a polymer having a vinyl alcohol unit of 70 mol% or more, and the polyvinyl alcohol generally has an average degree of polymerization of 50 to 1,500,000,
Preferably it is 200 to 20,000, and the saponification value is 60 to
100%, preferably 90 to 100%, more preferably 98 to 100% is used. As other polymers, in addition to vinyl alcohol units and vinyl acetate monomers, ethylene, itaconic acid, vinylamine, acrylamide, vinyl pivalate, maleic anhydride, and sulfonic acid-containing vinyl compounds are obtained by copolymerization. May be used.

The above pH-adjusted heated zirconia solution, a vinyl alcohol-containing water-absorbing organic polymer and a solvent are mixed to prepare the water-absorbing coating composition,
When a hygroscopic film is formed, the mixing method is not particularly limited, and it suffices that the mixing be performed until the liquid is stirred and becomes uniform. In addition, the pH as described above
Instead of re-adjusting, a heated zirconia solution, a vinyl alcohol-containing water-absorbing organic polymer and a solvent were mixed and reacted, and then the solution was adjusted to pH 2.5 to 5 with an anion exchange resin or the like. There is no problem in preparing the composition. In this mixing, when the mixing ratio of the (a) heated zirconia solution and the (b) vinyl alcohol-containing water-absorbing organic polymer is set, the molar concentration of (a) [a] and (b) [A] / [b, which is the ratio to the molar concentration of the vinyl alcohol unit present [b1]
1] is preferably in the range of 0.2 to 0.4.

The molar concentration [a] of the above (a) is the molar concentration in the composition obtained by dividing the weight of the zirconium compound in the composition by the molecular weight of the zirconium compound. And the molar concentration [b1] of the vinyl alcohol present in (b) is defined as the composition obtained by dividing the weight of only the vinyl alcohol unit in the composition by the molecular weight of the vinyl alcohol unit. It is the molar concentration in a substance. For example, in the case of polyvinyl alcohol, the weight of the vinyl alcohol unit is obtained by multiplying the total weight of the polyvinyl alcohol by the degree of saponification to obtain the total weight of the vinyl alcohol, and dividing this by the molecular weight of the vinyl alcohol unit to obtain [b1]. Also, even when other monomers are polymerized, calculate the weight excluding other monomers including the vinyl acetate monomer other than the vinyl alcohol unit from the total weight, divide this by the molecular weight of the vinyl alcohol unit, [ b1]. The value obtained by dividing this [a] by [b1] is [a]
/ [B1]. [A] / [b1] is 0.2 to 0.
When it is in the range of 5, it is desirable in that a film having a cleaning property is obtained, and when it is in the range of 0.2 to 0.4, it is possible to obtain a film having antifogging property and cleaning property at the same time. desirable. Furthermore, [a] / [b1] is 0.25 to 0.32
It is particularly preferable that the thickness be in the range described above, since a film having high film strength can be obtained.

The solvent used in the present invention includes water or toluene, which is generally called an organic solvent,
Aromatic solvents such as xylene and aliphatic solvents such as glycerin are used. Is preferred. This organic solvent is often used with water. The amount of the solvent used is preferably 10 to 100 parts by weight based on a total of 100 parts by weight of the zirconium compound and the vinyl alcohol-containing water-absorbing organic polymer.
00 parts by weight, more preferably about 800 to 200 parts by weight.
0 parts by weight.

The catalyst used in the present invention includes a hydrolysis catalyst and a curing catalyst. The hydrolysis catalyst is used for a hydrolysis reaction of a zirconium compound. Therefore, if a zirconium compound is previously hydrolyzed to some extent and polycondensed to use a polymer having an OH group, a hydrolysis catalyst may not be necessary.

As the hydrolysis catalyst, hydrochloric acid, sulfuric acid,
A mineral acid such as nitric acid is 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. These hydrolysis catalysts are used in an amount of 0.0 parts per 100 parts by weight of the zirconium compound.
It is 1 to 0.5 part by weight, preferably 0.015 to 0.3 part by weight. If the amount is less than 0.01 part by weight, the hydrolysis may be insufficient. If the amount exceeds 0.5 part by weight, the polycondensation reaction may proceed, and the viscosity may increase.

As the curing catalyst, inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia are also used as catalysts. These polymerization 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 zirconium compound. If the amount is less than 0.01 part by weight, the hydrolysis may be insufficient. If the amount exceeds 0.5 part by weight, the polycondensation reaction may proceed, and the viscosity may increase.

The curing catalyst is mainly used as a catalyst for the polycondensation reaction of a zirconium compound, and as a catalyst for a crosslinking reaction of a water-absorbing organic polymer.
It is used as a catalyst for a polycondensation reaction and / or a cross-linking reaction between a polymer having a group, a zirconium compound, and a water-absorbing organic polymer. 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 salt includes 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.

As the metal acetylacetonate,
Examples include aluminum acetylacetonate, indium acetylacetonate, chromium acetylacetonate, titanium acetylacetonate, and cobalt acetylacetonate.

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.

Examples of the peroxide include hydrogen peroxide.

The perchloric oxide includes 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, triphosphoric acid, polyphosphoric acid, metaphosphoric acid, trimetaphosphoric acid , Tetrametaphosphoric 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, sulfite, 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, Examples thereof include iodic acid, hypoiodic acid, permanganic acid, manganic acid, pertechnetic acid, technetic acid, perrhenic acid, rhenic acid, and the like, and salts thereof.

The amount of the curing catalyst used is preferably 0.01 to 2 parts by weight, more preferably 100 parts by weight of the total amount of the zirconium compound and the water absorbing organic polymer in the water absorbing coating composition. Preferably, 0.
05 parts by weight. If the amount is more than 2 parts by weight, the polycondensation proceeds rapidly, so that it becomes difficult to dissolve in the organic solvent, and the resulting coating becomes non-uniform, so that the strength may be reduced.

The water-absorbing coating composition may further contain at least one water-absorbing inorganic composition. As the water-absorbing inorganic composition, sepiolite,
Silica gel and the like. Further, the water absorbing coating composition may further contain at least one kind of polyacrylic acid. Examples of the polyacrylic acids include polyacrylic acid, polymethacrylic acid, and salts thereof. The amount of the polyacrylic acid to be used is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the water-absorbing coating composition. 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 the water-absorbing coating composition 10.
It is preferable to use 0.1 to 0.5 parts by weight with respect to 0 parts by weight. If it exceeds 0.5 parts by weight, the hardness of the film formed by the composition obtained may be low.

In the present invention, the water-absorbing coating composition may further contain a fluorine-containing surfactant containing a hydrophilic group. Are, for example, perfluoroalkyl carboxylate, perfluoroalkyl ammonium salt, perfluoroalkyl betaine, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl group-containing oligomer, trifluoropropyl trichlorosilane, trifluoropropyl bromosilane, trifluoro Propyltrimethoxysilane, trifluoropropyltriethoxysilane, heptadecafluorooctyltrimethoxysilane, heptadecafluorooctyltriethoxysilane, and the like can be suitably used.

Further, in the present invention, a heat ray absorbing material may be contained in the water-absorbing coating composition. The rise can be suppressed, and the temperature of the glass surface can be increased to make it difficult for water droplets to adhere. Silver ions can be suitably used as the heat ray absorbing material.

Further, in the present invention, a heat storage material may be further contained in the water-absorbing coating composition to accumulate radiant heat such as sunlight to keep the temperature of the glass surface high and to prevent water droplets. Adhesion can be reduced. As the heat storage material, high-density polyethylene, paraffin, or the like can be suitably used.

Further, in the present invention, an ultraviolet absorber may be contained in the water-absorbing coating composition, and if it is used for a transparent material such as glass, it will block short-wavelength sunlight harmful to the human body. it can.

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 water-absorbing coating composition, so that the generation and propagation of mold and bacteria can be prevented. Antibacterial agents include sodium sulfonate, isothiazoline, benzoic acid, 10,10-oxybisphenoxyarsine,
-(4-thiazolyl) -benzimidazole, N- (fluorodichloromethylthio) -phthalimide, 2-methylcarbonylaminobenzimidazole, silver, copper,
Examples include zeolite, silver zirconium phosphate, silver hydroapatite, silver phosphate glass, silver phosphate ceramic, and the like.

In the present invention, the water-absorbing coating composition forming the surface layer of the member may be a composition in which silicone or silica forming an inorganic skeleton and a zirconium compound or zirconia and photocatalyst particles are dispersed. When the photocatalyst is photoexcited, the surface of the silicone or silica is highly hydrophilized, and moisture in the air is chemically adsorbed on the surface of the member in the form of hydroxyl groups. The condensed water and water droplets thus adhered are quickly turned into a water film and spread uniformly on the surface, so that the surface exhibits a high degree of anti-fogging property. The silicone and silica mentioned here are not particularly limited, and any commonly used silicone and silica may be used. In addition, hydrophobic contaminants and the like are difficult to adhere to the surface of the member, and even if it adheres, the adhesion is unstable, and further, as a result of the oxidative decomposition action of the photocatalyst, the adhered matter is easily decomposed, It detaches and the member surface is maintained in a clean state. The following photocatalyst particles can be used. As the light to be irradiated, when the photocatalyst particles are anatase-type titanium oxide, rutile-type titanium oxide, zinc oxide, strontium titanate, sunlight, indoor lighting, a fluorescent lamp, a mercury lamp, an incandescent lamp,
Light from a xenon lamp, a high-pressure sodium lamp, a metal halide lamp, or a BLB lamp is preferred. When the photocatalyst particles are tin oxide, light from a solar germicidal lamp, a BLB lamp, or the like is preferable. Further, the illuminance of the irradiated light may be appropriately determined in consideration of the composition of the member, its use, and the like.However, in order for the hydrophilic portion of the substrate surface to be highly hydrophilized and to maintain the state, And the illuminance of the excitation light is 0.
It is preferably 001mW / cm ² or more, more preferably 0.01 mW / cm ² or more, most preferably 0.1 mW / cm ² or more. Further, according to a preferred embodiment of the present invention, it is preferable to add a metal such as Ag, Cu, or Zn to the photocatalytic coating composition layer. The surface layer to which such a metal is added can kill bacteria and fungi attached to the surface even in a dark place, and thus can further improve antifouling properties.

According to another preferred embodiment of the present invention, Pt, Pd,
Platinum group metals such as Ru, Rh, Ir, Os can be added. The surface layer to which such a metal is added,
The redox activity of the photocatalyst can be enhanced, and the decomposability of organic dirt and harmful gas and odor can be improved. In the present invention, there is provided a member in which the surface of a substrate is coated with a transparent water-absorbing coating composition comprising a composite polymer in which organic molecules are crosslinked to an inorganic skeleton. The water-absorbing coating composition is composed of an inorganic polymer and an organic polymer cross-linked to each other, and the surface layer of the member is covered with a highly durable film insoluble in water and an organic solvent. Therefore, the member coated with this composition has antifogging property, antifouling property, dewproofing property, and humidity control property.

As described above, the anti-fogging property means that, for example, in the case of a mirror, when minute water droplets such as steam come into contact with the film surface of the member, the surface layer is formed without dew condensation on the surface. Since it reaches and is absorbed by the water-absorbing organic polymer in the water-absorbing coating composition to be formed, it means that clouding can be prevented and the visibility of the reflected image can be maintained.

As described above, the anti-dew property means that the surface layer of the substrate has a function of preventing the following phenomena. The phenomenon is that when small water droplets such as steam come into contact with the surface of the member, it is rapidly cooled due to the difference in temperature between the air and the surface layer, and the water droplets are condensed, and the size can be visually determined. This is a phenomenon that water droplets are formed and adhere to the substrate surface layer. The antifouling property is not only that the film itself has a structure that does not easily become dirty, but that it can be easily removed even if it becomes dirty, and that there is no problem that the film will be damaged even if washed with detergent etc. Means

As described above, the humidity control means having a function of keeping the humidity around the member constant.

The average particle size of the fine ZrO ₂ particles in the composition is preferably in the range of 0.5 nm to 40 nm. More preferably, the range is 0.5 nm to 5 nm. When the average particle size is less than 0.5 nm, the film strength is reduced and the appearance during film formation is deteriorated. For example, when zirconium nitrate or the like is used, coloring is likely. In addition, the viscosity change of the composition also becomes sharp. Also, 100
ZrO ₂ having an average particle diameter exceeding nm causes deterioration of the transparency of the formed coating film. By the way, the particulate ZrO ₂ in the composition is derived from zirconyl such as zirconium nitrate, and long-time heating of this material in an aqueous solution at 50 ° C. or more can increase its particle size. If the pH is set to be as neutral as possible with an anion exchange resin or the like before heating, heating can increase the particle size more quickly. These facts are as described above, but the method of producing the fine-particle ZrO ₂ is not particularly limited to the above-mentioned method, and is produced by another method using pressure or the like. But it is good.

As the particulate inorganic oxide, oxides such as yttrium oxide, niobium oxide and cerium oxide can be used in addition to titania, silica, alumina and zirconia. The particulate inorganic oxide to be mixed into the composition preferably has an average particle size in the range of 5 nm to 200 nm, and more preferably has an average particle size in the range of 40 nm to 100 nm. In addition, the shape of the chain is preferably a chain shape rather than a granular shape because the shape of the resulting coating film is better in terms of transparency. The optimal addition amount of these particulate inorganic oxides varies depending on the amount of the zirconium compound, but as the zirconium compound amount, [a] / [b1] is in the range of 0.2 to 0.4. In the composition, the amount is preferably 10 to 50 parts by weight, more preferably 20 to 40 parts by weight, based on 100 parts by weight of the vinyl alcohol-containing water-absorbing organic polymer. Also,
Depending on the amount of the inorganic oxide added and the average particle diameter, even in the composition having [a] / [b1] of 0.2 or less, a film having good scratch resistance and cleanability and little discoloration can be obtained. May be obtained.

Among the particulate inorganic oxides, silica is the best in terms of alkali resistance and water resistance as compared with alumina and titania. Examples of the finely divided silica include silica sol. 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, those having an average particle diameter of 5 to 200 nm are used.
If the dispersion state is poor, and if it exceeds 200 nm, the transparency of the resulting coating film will be poor.

The addition of the above-mentioned formaldehyde has the merit that it is hard to be attacked by strong alkali chemicals because the polyvinyl alcohol is formalized. In addition, chemical resistance is improved by acetalization, benzalization, butyralization with an aldehyde compound such as acetaldehyde, and the like. These aldehyde compounds are used in an amount of 10 to 50 parts by weight, preferably 15 to 30 parts by weight, based on a total of 100 parts by weight of the zirconium compound and the vinyl alcohol-containing water-absorbing organic polymer.

According to the present invention, the member is formed, for example, as follows. First, the components of the water-absorbing coating composition are mixed to obtain a transparent to translucent coating solution. Next, this coating solution is coated on at least one surface of the member, and the coated member is heated and dried at a temperature of 80 ° C. or higher, preferably in a range of 120 ° C. to 200 ° C., to obtain a coated member of the present invention. If necessary, the heat treatment may be performed after coating the coating liquid several times. Further, the number of times of heating may be 2 bake or more, and the film may be naturally dried at room temperature before heating, and may be heated after removing a certain amount of water from the inside of the film.

The coating method is not particularly limited, and any coating method such as a bar coat, a die coat, a curtain coat, and a roll coat can be used. Since the composition can be coated by curtain flow coating even on a veneer such as a mirror, coating can be quickly performed on a veneer such as a considerably large veneer. Therefore, a curtain coat is preferred. The thickness of the film obtained in this way is not particularly limited, but is preferably 5 to 20 μm, more preferably 8 to 12 μm when performing only one coating.

When the composition is applied to the surface of a member and the composition is dried or cured, the composition is heated from 80 ° C. to 17 ° C.
At the stage of drying or curing at the set temperature of 0 ° C,
Once the temperature is returned to the normal temperature, the member is returned to the normal temperature, and then is heated again at the original set temperature to completely cure the film. In this case, for example, when forming a coating of 8 μm class, a completely cured coating without discoloration of the coating can be obtained by a heating operation such as drying at 150 ° C. for 10 minutes, natural cooling at room temperature and drying for 20 minutes. That is, such an effect can be obtained by heating with one coat and two bake. In this case, the time distribution is not particularly limited. The effect of preventing the discoloration of the coating can be obtained by providing a temporal change in the set temperature such as lowering the set temperature by 10 ° C. or more for a certain period of time during the heating operation.

When the composition is applied to the surface of a member and the composition is dried or cured, the composition is dried or cured at a low temperature, washed with water and / or an organic solvent, and then heated again at a high temperature. By drying or curing with the above, discoloration of the film can be prevented. In the present invention, as the organic solvent,
Aromatic solvents such as toluene and xylene, which are generally called organic solvents, and aliphatic solvents such as glycerin are used. In particular, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, and the like are used. Organic solvents that are compatible with water are preferred. This organic solvent is often used with water. The low temperature is not particularly limited as long as the composition does not flow out with water and does not color.
Preferably at 50-100 ° C, more preferably 8
0-100 ° C. The high temperature is not particularly limited as long as the composition can maintain the desired anti-fog performance and durability, and is preferably 100 to 180 ° C.
The temperature is more preferably 130 to 150 ° C. Further, as a washing method with water and / or an organic solvent,
There is no particular limitation as long as a sufficient cleaning effect can be obtained. For example, water can be directly discharged onto the surface of the composition with a tube hose.

When the composition is applied to the surface of a component and the composition is dried or cured, the heat source is preferably located on the side opposite to the painted surface of the component. This makes it possible to shorten the heating time. The type of the heat source at this time is not particularly limited, such as a far-infrared lamp, a near-infrared lamp, an electric heater, etc., and its heat capacity and installation position are not particularly limited. Condition. In addition, a near-infrared lamp is more preferable as a heat source in terms of dust protection because circulation of air around the member is less necessary.

After the composition is applied to the surface of a member, and the composition is dried or cured, the member is immersed in water for a certain period of time or more, whereby the antifogging performance can be improved. By performing this operation, the film is swollen with water,
The purpose is to make it easy to take in moisture into the film. The longer the immersion time is, the better, but at least 10 minutes is required. As a method for completing this operation in a short time, there is a steam cleaning operation.
This operation aims at obtaining the same effect as the water immersion operation by uniformly applying steam generated by the boiler to the member surface for 10 seconds or more. There is no particular limitation on the operation method at this time, but it is necessary to change the method according to the member so that the steam is uniformly applied to the entire surface of the member.

The member may be provided with a dryer including a heater and a blower. In this case, by providing a dryer in the vicinity of the member, the water absorbing ability of the water-absorbing coating composition can be remarkably improved, and higher dew-proofing and anti-fog effects can be obtained. In addition, by controlling the water absorption rate of the water absorbing coating composition, the humidity of the atmosphere can be adjusted.

According to the present invention, when the substrate surface is coated with the water-absorbing coating composition, the surface of the member is washed in advance with a detergent to remove impurities on the surface of the substrate and to enhance the hydrophilicity of the member. Can be As a result, no air bubbles enter between the member and the coating, and a coating with high adhesion is obtained, and further, the alkali resistance of the coating is improved.

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. Means a physical treatment for the purpose of polishing and improving the smoothness of the substrate surface. For example, in the case of coating the mirror with the water-absorbing coating composition, the washing is preferably washing with ceria polishing. This is achieved by dissolving particles containing ceria as a main component in a neutral detergent or the like to prepare a detergent and washing the substrate surface thereby, thereby improving the hydrophilicity by degreasing or smoothing the substrate surface. be able to.

In the present invention, as described above, by preliminarily hydrophilizing, the wettability of the substrate 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 surface of the substrate by discharge or the like is considered as a method. Among them, particularly, when the substrate is subjected to a corona discharge surface treatment, the coating liquid is coated, Hydrophilicity 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 high-speed and low-speed electrons in the air gap collide with oxygen atoms by corona discharge on the surface of the member to generate excited oxygen molecules, which are converted into ozone, highly reactive oxygen atoms and free radicals. Change. The active species can oxidize the surface of the member and improve the wettability of the coating liquid. In this way, by modifying the surface of the member, the adhesion between the coating composition, which is another polar molecule, and the member can be promoted, and as a result, the adhesion can be improved.

In preparing the member, the substrate on which the composition can be coated is not particularly limited, and examples thereof include metal, ceramics, glass, plastic, wood, stone, cement, concrete, fiber, cloth, and the like. And their laminates can be suitably used. The substrate may be determined in consideration of the use of the member. The mirror as the member is a mirror made of a glass base material provided with a reflection coat on the back surface,
A mirror made of a transparent plastic with a reflective coat on the back surface, a mirror with a reflective coat on the surface of a base material such as plastic, glass, metal, etc., a reflective coat on the base material surface of plastic, glass, metal, etc. A mirror with a transparent hard coat on it, a mirror made of a mirror-polished metal substrate,
A mirror having a transparent hard coat provided on the surface of a mirror made of a mirror-polished metal base material, a mirror having a transparent hard coat provided on a transparent plastic base material provided with a reflective coat on the back surface, or the like can be suitably used. The transparent plate-shaped member as the member,
Plastic members such as polyethylene terephthalate, polyvinyl chloride, and methacrylic resin, and plate glass such as soda-lime glass, borosilicate glass, and aluminosilicate glass can be suitably used. The transparent lens as the member, polyethylene terephthalate,
Plastic members such as polyvinyl chloride and methacrylic resin, and glass such as soda-lime glass, borosilicate glass, and aluminosilicate glass can be suitably used. As the transparent film as the member, a plastic member such as polyethylene terephthalate, polyvinyl chloride, and methacrylic resin can be suitably used. The members are not limited to the members described above. A transparent intermediate layer may be provided between the substrate and the surface layer for the purpose of improving adhesion to the substrate and the like.

Further, the surface layer may be further covered with a porous hard coat film, thereby improving abrasion resistance and weather resistance and reducing reflected light.
The surface of the hygroscopic mirror according to the present invention has a hard film having a pencil hardness of about H to 4H or more.

The mirror as the member according to the present invention can be used for an automobile side mirror, an automobile interior mirror, a mirror installed in a bathroom or a washroom, and the like. In particular, in consideration of the water absorption capacity of the anti-fog mirror of the present invention, the mirror can be suitably used in a washroom where steam from hot water supply adheres to the surface and is easily clouded.

Further, the transparent plate-like member as the member can be used for 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. Further, as the transparent lens as the member, it can be used for glasses, goggles, lenses for cameras, lenses for portable video cameras, lenses for astronomical telescopes, and the like. further,
As the transparent film as the member, food wrapping paper, car side mirrors, car room mirrors,
It can be used as an anti-fog film to be attached to a mirror installed in a bathroom or a toilet. In addition, the member is preferably used as any of ceiling materials for bathrooms having antifouling properties and dewproofing properties, toilet pipes, water supply pipes, urinals, toilet bowls, toilet traps, wash bowls, wash traps. Available. Further, the member includes a bathtub having antifouling properties and dewproofing properties, a bathroom wall material, a bathroom flooring material, a bathroom grating, a shower hook, a bathtub handgrip, a bathtub apron, a bathtub drain plug, and a bathroom. Window,
Bathroom window frames, bathroom window floorboards, bathroom lighting fixtures, drainage plates,
Drainage pits, bathroom doors, bathroom door frames, bathroom window bars, bathroom door bars, slats, mats, soap boxes, tubs, bathroom mirrors, bath chairs, transfer boards, water heaters, bathroom storage shelves,
Bathroom handrails, bath lids, bathroom towel rails, bathroom chairs such as shower chairs, basins, kitchen kitchen backs, kitchen flooring, sinks, kitchen counters, drain baskets, dish dryers, dishwashers Bowl, stove, range hood,
Ventilation fan, stove ignition part, floor material for toilet, wall material for toilet,
Ceiling for toilet, ball tap, water stopcock, cigarette, toilet seat, elevator seat, toilet door, toilet key, toilet towel rail, toilet lid, handrail for toilet, counter for toilet, flush valve, tank , Toilet components such as water nozzles for toilet seats with flushing functions, toilet traps, toilet mirrors, washroom storage shelves, drain plugs, toothbrush stands, toilet mirror lighting fixtures, wash counters, water soap dispensers, washbasins, oral cavity Washer, hand dryer, washing tub, washing machine lid, washing machine pan, dehydration tub, air conditioner filter, touch panel, faucet fitting, cover of human body detection sensor, shower hose, shower head, shower -It can be suitably used for any of a water discharge section, a sealant, and a joint.

[0111]

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.

[0112] Alkali resistance performance evaluation method 1;
One drop is dropped on the surface of the film, left at rest in an atmosphere of 25 ° C. for 1 hour, washed away with water, and the state after the portion is examined. ；: Even if it blows on the trace, it does not become cloudy and no trace remains. Δ: The trace does not become cloudy even if the breath is blown, but the trace remains. ×: When the breath is blown on the trace, it becomes cloudy and the trace remains.

[0113] Alkali resistance performance evaluation method 2: A drop of 1 drop of Hiter (manufactured by Kao) on the membrane surface with a disposable 2 ml spoiler, allowed to stand at 25 ° C for 1 hour, then drained with water, Investigate later. ；: Even if it blows on the trace, it does not become cloudy and no trace remains. Δ: The trace does not become cloudy even if the breath is blown, but the trace remains. ×: When the breath is blown on the trace, it becomes cloudy and the trace remains.

Evaluation method of acid resistance performance: One drop of 2 ml of sun paul (made by Kincho) was dropped on the surface of the membrane with a disposable dropper, allowed to stand at 25 ° C. for 1 hour, poured with water, and washed with water. Investigate the situation. ；: Even if it blows on the trace, it does not become cloudy and no trace remains. Δ: The trace does not become cloudy even if the breath is blown, but the trace remains. ×: When the breath is blown on the trace, it becomes cloudy and the trace remains.

[0115] Antifogging performance evaluation method: The member coated with the coating is placed in an atmosphere at 30 ° C and 100% humidity, and the time required for the 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. A: Time until clouding is less than 2 minutes and 1 minute 30 seconds or more. ；: The time until clouding was from 1 minute to less than 1 minute 30 seconds. Δ: Time until clouding is 30 seconds or more and less than 1 minute. X: The time until clouding was less than 30 seconds.

Evaluation of appearance A: No air bubbles or turbidity was observed on the film surface. ；: The film surface has only bubbles or turbidity that are not noticeable. Δ: Some bubbles or turbidity are observed on the film surface. X: Air bubbles and cloudiness are quite conspicuous on the film surface.

Evaluation of Water Resistance The member coated with the coating was immersed in water at room temperature for 30 seconds, and the surface of the coating was scratched with a pencil having a pencil hardness of 2H.
After drying, the scratch marks are observed and evaluated. A: No scar is seen on the film surface. ○: no scar is seen on the film surface, but immediately after scratching,
Depressions are seen in the coating. However, those that cannot be seen when dried. Δ: No scar is seen on the film surface, but immediately after scratching,
Depressions are seen in the coating. In addition, those in which the depression of the coating does not heal even when dried ×: A scar is seen on the film surface.

Evaluation of Cleanability The member coated with the coating was immersed in water at room temperature for 10 minutes, and then the surface of the coating was wiped with a jersey cotton cloth. ；: No residual fiber of the cloth or scratches on the film surface. X: The residue of the fiber of the cloth and the scratch are considerably conspicuous on the film surface.

Evaluation of Coating Strength After the coated member was left in an atmosphere of 25 ° C. and 40-60% RH for 3 hours or more, a pencil scratch value of the coating surface was measured. evaluate. The evaluation method was the same as that described in the pencil scratch value measurement specified in JIS K 5400.

Measurement of Average Particle Size of Zirconia Particles The average particle size of zirconia in the heated zirconia solution was determined by
It is determined by measuring with a dynamic light scattering photometer DLS-600 (manufactured by Otsuka Electronics). The obtained value is the average particle size of zirconia in the coating composition.

Evaluation by Color Difference (ΔE) Measurement The degree of discoloration of the surface of the member to which the coating was applied was determined by using an 80 Colo
It is measured as a color difference (ΔE) on the surface of the member by an r Measuring System (manufactured by Nippon Denshoku Industries Co., Ltd.). 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 was not a concern in 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 Viscosity on the Second Day After Preparation of Coating Liquid The viscosity of the coating liquid is preferably as small as possible with time, and the viscosity range is optimally 0.1 to 1 Pa · s when a curtain coater is used. It is. Standard for evaluation by viscosity measurement on the second day after the preparation of the coating liquid. The viscosity is measured by a B-type viscometer (type BL, manufactured by Tokyo Keiki Co., Ltd.); 0.1 Pa · s ≦ the viscosity of the coating liquid on the second day after preparation <0.5 Pa · s; sufficient viscosity as the coating liquid Δ; 0.5 Pa · s ≦ the viscosity of the coating liquid on the second day after preparation <1 Pa · s; the storage stability as a coating liquid is insufficient, but the viscosity can be sufficiently used for a curtain coater ×; 1 Pa · s ≦ the second day after preparation. Coating liquid viscosity; insufficient viscosity as coating liquid

Evaluation of Defoaming Performance of Air Bubbles in Coating Solution When coating is performed by putting a 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 3cm length and 3mm width class,
Rotation speed of 1500 times per minute with multiple magnetic stirrer F-600 type (Micro 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 a stainless steel pipe, there is a possibility that the pipe and other metal parts which come into contact with the pipe are corroded. Therefore, a problem may occur in the durability of the machine used. Therefore, 80 ml of the coating liquid is put into a 100 ml beaker, and a member (stainless steel S) of the same material as the stainless steel pipe having a length of 5 cm, a width of 2 cm and a thickness of 3 mm class is placed therein.
US316) and hold for one week. One week later, the appearance changes are observed. Estimation of the possibility of pipe corrosion caused by the coating liquid; coating with a normal coating machine is possible without any change in appearance. ×: Change in appearance was observed, and painting with a normal coating machine was not possible.

Evaluation of Adhesion by Cross-cut Tape Method (Moisture Resistance Test) The member coated with the coating was immersed in warm water of 60 ° C. for 3 hours and then immersed in normal temperature water for 16 hours. After drying, a test was conducted to check the adhesion of the coating to the member by a cross-cut tape method. The evaluation method is JIS K 5400
The test was performed by the method described in the cross-cut tape method, which is a test for observing the adhesion of the paint general test method specified in (1). 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. ×: 21 or more out of 100 peeled portions on the film surface.

[0126]

Example 1 Zircosol ZN (manufactured by Daiichi Kagaku Kagaku Kogyo); 98.5 g and water (147.3 g) were added and stirred for 5 minutes, followed by ion exchange resin WA-20 (manufactured by Mitsubishi Kasei);
Mix 0 g and stir until the solution has a pH of 3.0. Thereafter, the solution and the ion exchange resin were separated by decantation, the separated solution was transferred to a sealed glass bottle, and the transferred solution was placed in a 95 ° C. oven (DK-400, manufactured by Yamato Scientific) using a magnetic stirrer. React for 5 hours with stirring. And normal temperature (25 ° C)
Let sit for one month. (Hereinafter referred to as A1 liquid)
To this solution was added ion exchange resin WA-20 (manufactured by Mitsubishi Kasei);
20 g is mixed again, the solution is stirred until the pH becomes 4.0, the solution and the ion-exchange resin are separated by decantation, and the solution is allowed to stand at room temperature (25 ° C.) for 1 hour. (Hereinafter referred to as A2 liquid.) On the other hand, PVA-105 (average degree of polymerization: 500, complete saponification type; saponification value: 98 to 99%)
(Kuraray); 90 g of water was added to 10 g, and the mixture was stirred at 90 ° C. for 5 hours to dissolve polyvinyl alcohol. (Hereinafter referred to as C1 solution) and A2 solution: 80 g
And C1 solution: 100 g, water: 56 g, ethanol: 56 g
And stirring at room temperature (25 ° C.) for 30 minutes to obtain a coating solution. This coating solution was coated once on one side of a mirror with an applicator, and heated and dried at 150 ° C. for 25 minutes in an oven (DK-400, manufactured by Yamato Scientific Co., Ltd.) to obtain a transparent coating film (film thickness: 8 μm). was gotten.

[0127]

[Example 2] A2 liquid of Example 1: 80 g and C1 liquid: 100
g, water: 56 g, and ethanol: 56 g are mixed and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating solution. Same as Example 1.

[0128]

Example 3 Solution A2 of Example 1: 80 g and Solution C1: 100
g, water: 56 g, and ethanol: 56 g are mixed and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating solution, except that the A2 solution is changed from 80 g to the A2 solution to 70 g. Same as Example 1.

[0129]

Example 4 Solution A2 of Example 1: 80 g and solution C1: 100
g, water: 56 g, and ethanol: 56 g are mixed and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating solution. Except that the A2 solution: 80 g and the A2 solution: 65 g are used. Same as Example 1.

[0130]

[Example 5] Solution A2 of Example 1: 80 g and solution C1: 100
g, water: 56 g, and ethanol: 56 g are mixed and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating solution, except that A2 solution: 80 g and A2 solution: 60 g. Same as Example 1.

[0131]

Example 6 Solution A2 of Example 1: 80 g and Solution C1: 100
g, water: 56 g, and ethanol: 56 g are mixed and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating solution, except that A2 solution: 80 g and A2 solution: 85 g. Same as Example 1.

[0132]

[Example 7] 80 g of A2 solution and 100 g of C1 solution of Example 1
g, water: 56 g, and ethanol: 56 g are mixed and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating solution, except that A2 solution: 80 g and A2 solution: 90 g. Same as Example 1.

[0133]

Example 8 A2 solution of Example 1: 80 g and C1 solution: 100
g, water: 56 g, and ethanol: 56 g are mixed and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating solution, except that A2 solution: 80 g and A2 solution: 95 g. Same as Example 1.

[0134]

Example 9 A2 solution of Example 1: 80 g and C1 solution: 100
g, water: 56 g, and ethanol: 56 g are mixed and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating solution. When the coating solution is obtained, 80 g of the A2 solution and 100 g of the A2 solution are obtained.
Same as Example 1 except that

[0135]

Example 10 A2 liquid of Example 1: 80 g and C1 liquid: 10
0 g, 56 g of water, and 56 g of ethanol were mixed and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating solution. Then, 80 g of the A2 solution and 105 of the A2 solution were obtained.
Same as Example 1 except for g.

[0136]

Example 11 Solution A2 of Example 1: 80 g and Solution C1: 10
0 g, water: 56 g, and ethanol: 56 g were mixed and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating solution. When the coating solution was obtained, 80 g of the A2 solution and 110 g of the A2 solution were obtained.
Same as Example 1 except for g.

[0137]

Example 12 The process of preparing liquid A2 in Example 1 was carried out by adding the ion exchange resin WA-20 (manufactured by Mitsubishi Kasei) to the liquid A1;
And stirred until the solution reaches pH 3.0,
The solution and the ion-exchange resin were separated by decantation and replaced with a process of allowing the solution to stand at room temperature (25 ° C.) for 1 hour. A2 solution was mixed with C1 solution, water and ethanol were mixed together in A2. Liquid: 80 g and C1 liquid: 100 g,
Water: except that instead of mixing 112 g of the three solutions
Same as Example 1

[0138]

Example 13 The process of preparing liquid A2 in Example 1 was carried out by adding the ion exchange resin WA-20 (manufactured by Mitsubishi Kasei) to the liquid A1;
And stirred until the solution is at pH 3.5,
The solution and the ion exchange resin are separated by decantation, and the process is allowed to stand at room temperature (25 ° C.) for 1 hour, and the A2 solution and the C1 solution, water, and ethanol of Example 1 are mixed. However, solution A2: 80 g and solution C1:
Same as Example 1 except that three solutions of 100 g, 112 g of water were mixed.

[0139]

Example 14 The process of preparing solution A2 of Example 1 was performed by adding the ion exchange resin WA-20 (manufactured by Mitsubishi Kasei) to solution A1;
And stirred until the solution has a pH of 2.5,
The solution and the ion-exchange resin were separated by decantation and replaced with a process of allowing the solution to stand at room temperature (25 ° C.) for 1 hour. A2 solution was mixed with C1 solution, water and ethanol were mixed together in A2. Liquid: 80 g and C1 liquid: 100 g,
Water: except that instead of mixing 112 g of the three solutions
Same as Example 1

[0140]

Example 15 The process of preparing the solution A1 in Example 1 was carried out by adding 98.5 g of zircosol ZN (manufactured by Daiichi Kagaku Kagaku Kogyo) and 147.3 g of water and stirring for 5 minutes. 20 (manufactured by Mitsubishi Kasei); 60 g was mixed therein, and the solution was stirred until the solution reached pH 3.0. Then, the solution and the ion exchange resin were separated by decantation, and the separated solution was transferred to a sealed glass bottle. The transferred solution was reacted in a 95 ° C. oven (DK-400, manufactured by Yamato Scientific Co., Ltd.) for 5 hours with stirring using a magnetic stirrer, except that the process was changed to the process of adding 0.13 g of 3% aqueous ammonia. Same as Example 1

[0141]

Example 16 The process of preparing the A1 solution in Example 1 was carried out by adding 98.5 g of zircosol ZN (manufactured by Daiichi Kagaku Kagaku Kogyo) and 147.3 g of water and stirring the mixture for 5 minutes. 20 (manufactured by Mitsubishi Kasei); 60 g was mixed therein, and the solution was stirred until the solution reached pH 3.0. Then, the solution and the ion exchange resin were separated by decantation, and the separated solution was transferred to a sealed glass bottle. The transferred solution is reacted in a 95 ° C. oven (DK-400, manufactured by Yamato Scientific Co., Ltd.) for 5 hours while stirring using a magnetic stirrer, except that the process is to add 0.13 g of 3% hydrogen peroxide solution. Same as in Example 1

[0142]

Example 17 The process of preparing the A1 solution in Example 1 was carried out by adding 98.5 g of zircosol ZN (manufactured by Daiichi Kagaku Kagaku Kogyo) and 147.3 g of water, and stirring for 5 minutes to obtain 9% nitric acid. A mixture of 80 g of a zirconium solution, 4 g of yttrium nitrate (manufactured by Wako Pure Chemical Industries), and 36 g of water obtained by mixing and stirring the yttrium nitrate solution for 5 minutes was ion-exchange resin WA-20 (manufactured by Mitsubishi Kasei); After stirring until the solution reaches pH 3.0, the solution and the ion exchange resin are separated by decantation, the separated solution is transferred to a sealed glass bottle, and the transferred solution is placed in an oven at 95 ° C. (DK-400, manufactured by Yamato Scientific Co., Ltd.) using a magnetic stirrer to stir the reaction for 5 hours.
The two solutions were mixed to form a transparent coating film (film thickness: 8).
μm) is obtained when A2 solution: 80 g and C1 solution:
100 g, 28 g of water and 28 g of ethanol are mixed to form a transparent coating film (film thickness: 12 μm).
m) is the same as in Example 1, except that

[0143]

Example 18 Solution A2 of Example 1: 80 g and solution C1: 1
A solution prepared by adding 80 g of zirconyl acetate (manufactured by Daiichi Kagaku Kagaku Kogyo Co., Ltd.) and 145 g of water to the process of mixing four solutions of 00 g, 56 g of water, and 56 g of ethanol (hereinafter referred to as B1) The same as in Example 1 except that a step of adding 1 g of

[0144]

Example 19 98.5 g of zircosol ZN (manufactured by Daiichi Kagaku Kagaku Kogyo) and 147.3 g of water were added, and the mixture was stirred for 5 minutes, followed by ion exchange resin WA-20 (manufactured by Mitsubishi Kasei);
Mix 0 g and stir until the solution has a pH of 3.0. Thereafter, the solution and the ion exchange resin were separated by decantation, the separated solution was transferred to a sealed glass bottle, and the transferred solution was placed in a 95 ° C. oven (DK-400, manufactured by Yamato Scientific) using a magnetic stirrer. React for 5 hours with stirring. And normal temperature (25 ° C)
And leave still for one month to prepare solution A1. Further, 80 g of zirconyl acetate (manufactured by Daiichi Kagaku Kagaku Kogyo) and 145 of water
g is added and stirred for 5 minutes to prepare solution B1. Next, A
One solution: 100 g and B1 solution: 8 g are mixed and stirred for 5 minutes. Then, 20 g of ion-exchange resin WA-20 (manufactured by Mitsubishi Kasei) was mixed into the solution, and the solution was stirred until the solution became pH 4.0. The solution and the ion-exchange resin were separated by decantation, and the mixture was cooled to room temperature ( (25 ° C.) for 1 hour. (Hereinafter referred to as AB1 liquid) On the other hand, PVA-105
(Average degree of polymerization: 500, completely saponified; saponification value: 98
-99%) (manufactured by Kuraray); 10 g, water; 90 g,
Stir at 90 ° C. for 5 hours to dissolve polyvinyl alcohol to prepare solution C1. And AB1 solution:
80 g, C1 solution: 100 g, B1 solution: 1 g, water: 56
g, ethanol: five solutions of 56 g were mixed and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating solution. This coating solution is coated on one side of the mirror once with an applicator, and then coated in an oven (DK-400,
(Yamato Scientific Co., Ltd.) and dried at 150 ° C. for 25 minutes to obtain a transparent coating film (film thickness: 8 μm).

[0145]

Example 20 The process of preparing the solution A1 in Example 1 was carried out by adding 98.5 g of zircosol ZN (manufactured by Daiichi Kagaku Kagaku Kogyo) and 147.3 g of water and stirring for 5 minutes. 20 (manufactured by Mitsubishi Kasei); 60 g was mixed therein, and the solution was stirred until the solution reached pH 3.0. Then, the solution and the ion exchange resin were separated by decantation, and the separated solution was transferred to a sealed glass bottle. Same as Example 1 except that the transferred solution was reacted in a 95 ° C. oven (DK-400, manufactured by Yamato Scientific Co., Ltd.) for 10 hours while stirring using a magnetic stirrer.

[0146]

Example 21 The process of preparing the solution A1 in Example 1 was carried out by adding 98.5 g of zircosol ZN (manufactured by Daiichi Kagaku Kagaku Kogyo) and 147.3 g of water and stirring for 5 minutes. 20 (manufactured by Mitsubishi Kasei); 60 g was mixed therein, and the solution was stirred until the solution reached pH 3.0. Then, the solution and the ion exchange resin were separated by decantation, and the separated solution was transferred to a sealed glass bottle. Same as Example 1 except that the transferred solution was reacted in a 95 ° C. oven (DK-400, manufactured by Yamato Scientific Co., Ltd.) for 15 hours while stirring using a magnetic stirrer.

[0147]

Embodiment 22 A2 solution: 80 g and C1 solution: 1 in Example 1
In the process of mixing four solutions of 00 g, water: 56 g, and ethanol: 56 g, the A2 solution was adjusted to 60 g and colloidal silica Snowtex OUP (particle diameter: 40 to 50 g).
100, chain, manufactured by Nissan Chemical Industries) Same as Example 1 except that a step of mixing 30 g was added.

[0148]

Embodiment 23 A2 solution: 80 g and C1 solution: 1 in Example 1
Formaldehyde (manufactured by Wako Pure Chemical Industries, Ltd.) 4 in the process of mixing the four solutions of 00 g, 56 g of water and 56 g of ethanol.
Same as Example 1 except that a step of mixing 0 g was added

[0149]

Example 24 When the obtained coating solution was applied once on a mirror, the surface of the mirror was thoroughly washed with a 10% solution of mama lemon (manufactured by Kao) moistened with jersey cotton, and then washed with water. Wash and remove the mama lemon from the mirror surface, and apply the coating liquid to the mirror surface. Other steps are the same as those in the first embodiment.

[0150]

Embodiment 25 When the obtained coating solution is applied once on a mirror, the surface of the mirror is polished in advance with a ceria solution moistened with jersey cotton and then washed with water to wash off the ceria from the mirror surface. And apply the coating liquid to the mirror surface. The ceria liquid is Mirake A (Mitsui Metal Mining),
A suspension obtained by mixing 100 g with water; 900 g. Other steps are the same as those in the first embodiment.

[0151]

Example 26 When the obtained coating solution was applied once on a mirror, the surface of the mirror was thoroughly washed with a 10% aqueous solution of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) moistened in advance with jersey cotton. Then, the mirror is washed with water to remove sodium hydroxide from the mirror surface, and the mirror surface is coated with a coating liquid. Other steps are the same as those in the first embodiment.

[0152]

Example 27 When the obtained coating solution was applied once on a mirror, the surface of the mirror was corona-discharged in advance with a corona discharge surface treatment device (AG1-021S; manufactured by Kasuga Electric Co., Ltd.). Apply coating liquid to mirror surface. Other steps are the same as those in the first embodiment.

[0153]

[Embodiment 28] Next, an example of the present method for manufacturing a mirror according to the present invention will be described. This example is not limited to mirrors alone, nor is its manufacturing method limited to the methods described herein. FIG. 2 shows a mirror manufacturing apparatus. Example 19
Prepare at least 30 liters of a coating liquid having the same composition as that prepared according to the above. First, thickness 5m
Prepare m mirrors and place them at the end of the belt conveyor () where the members are moved. Next, the roller belt is moved at a speed of 1 m / min class, and the pretreatment steam cleaning device ()
Through. Thus, steam at a temperature close to 100 ° C. is sprayed on the mirror surface to degrease dirt such as fingerprints on the mirror surface. Then, it passes through a pure water cleaning device (). Here, pure water is sprayed on the surface of the mirror which has been washed by steam washing, and the sewage after washing is washed away. Furthermore, it passes through the air knife device for draining () to blow off the moisture remaining on the mirror surface,
Perform simple drying. Next, move on to the painting process. Painting is performed with a flow coater (made by Anest Iwata) () which is a curtain coating device. This apparatus stores the coating liquid in a storage tank, circulates the piping with a viking pump, drops the coating liquid from a long and narrow slit-shaped hole like a curtain-shaped waterfall, and places the base material underneath. Is passed through a mirror at a certain speed using a special conveyor, and the coating liquid is put on the base material by a certain amount at a time. This ends the painting. The amount to be applied at this time depends on the composition of the coating liquid, but in the liquid of Example 19, it is preferably 15 g per 0.06 m2.
Next, the process proceeds to the heating / drying process. First, the solvent in the coating liquid after the coating is gradually evaporated under the heating conditions of 100 ° C. and 20 minutes by the indirect heating furnace (). Then, the coating is dried in the heating furnace () under heating conditions of 150 ° C. and 25 minutes. Next, the process proceeds to the post-treatment steam cleaning step. The member coming out of the heating furnace is guided to a post-treatment steam spraying device (), and, similarly to the pre-treatment steam cleaning device (), the coating on the member is blown with steam at a temperature close to 100 ° C. to swell the coating. This is the intended process. By going through this process, the anti-fog performance of the coating is easily exhibited. Then, similarly to the pretreatment, the anti-fog mirror is completed through the cooling water device and the air knife device. The coating method is not limited to the curtain coating method of this embodiment,
Even a single plate such as an m2 class large mirror can be coated with a substantially constant film thickness, and has the advantage of mass production in a short time.

[0154]

Example 29 Heating at 150 ° C. for 10 minutes in an oven (DK-400, manufactured by Yamato Scientific Co., Ltd.) for 25 minutes at 150 ° C., and then allowed to stand naturally until the coating reached room temperature. Finally, heating at 150 ° C for 20 minutes
Example 19 is the same as Example 19 except that the heating step of the coat 2 baking method is used.

[0155]

Example 30 In a heating / drying process at 150 ° C. for 25 minutes in an oven (DK-400, manufactured by Yamato Scientific Co., Ltd.), a far-infrared lamp was applied from the back of the mirror, and the surface temperature of the coating was 150 ° C. The radiation thermometer (IT-530S;
Same as Example 19 except that the measurement was performed with Horiba Seisakusho and applied for 5 minutes.

[0156]

Embodiment 31 A 0.06 m2 (200 * 300) mirror prepared in the same manner as in Embodiment 19 is added to a 40 liter bucket filled with water for an additional 10 minutes by a flooding step.

[0157]

Embodiment 32 A process of applying steam at a temperature close to 100 ° C. generated by a steam generator (boiler) to a 0.06 m2 (200 * 300) mirror made in the same manner as in Embodiment 19 for 20 seconds is added. What you did.

[0158]

Comparative Example 1 Ethyl silicate 40 (manufactured by Colcoat); 0.3 g and silane coupling agent SH6040
(Manufactured by Toray Dow Corning); 0.46 g, 2N-HC
l; 0.01 g; aluminum isopropoxide;
To a solution obtained by adding 0.05 g, 35% HCl; 0.04 g, water 0.09 g, ethanol; 0.40 g, N, N-dimethylbenzylamine; 0.01 g and stirring at 25 ° C. for 10 minutes, % Polyacrylic acid aqueous solution (number average molecular weight: 130,000); 20.04 g and methanol;
A solution obtained by mixing 178.60 g was added, and the mixture was added at 25 ° C.
For 2 minutes to obtain a clear coating solution. This coating solution was coated once on one side of a mirror with an applicator, and heated and dried at 150 ° C. for 25 minutes in an oven (DK-400, manufactured by Yamato Scientific Co., Ltd.) to obtain a transparent coating film (film thickness: 8 μm). was gotten.

[0159]

Comparative Example 2 Solution A2 of Example 1: 80 g and Solution C1: 10
0 g, 56 g of water, and 56 g of ethanol were mixed and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating solution. When the coating solution was obtained, 80 g of the A2 solution and 115 of the A2 solution were obtained.
Same as Example 1 except for g.

[0160]

Comparative Example 3 Solution A2 of Example 1: 80 g and Solution C1: 10
0 g, water: 56 g, and ethanol: 56 g were mixed and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating solution. When the coating solution was obtained, 80 g of the A2 solution and 55 g of the A2 solution were obtained.
Same as Example 1 except that

[0161]

Comparative Example 4 Zircosol ZN (Daiichi Kagaku Kagaku Kogyo); 98.5 g and water (147.3 g) were added, and the mixture was stirred for 5 minutes, and then ion-exchange resin WA-20 (Mitsubishi Kasei);
Mix 0 g and stir until the solution has a pH of 3.0. Thereafter, the solution and the ion exchange resin were separated by decantation, the separated solution was transferred to a sealed glass bottle, and the transferred solution was placed in a 95 ° C. oven (DK-400, manufactured by Yamato Scientific) using a magnetic stirrer. React for 5 hours with stirring. And normal temperature (25 ° C)
For 24 hours to prepare solution A1. Then, 20 g of ion exchange resin WA-20 (manufactured by Mitsubishi Kasei) was added to this solution.
Is mixed again, the solution is stirred until the pH becomes 4.0, the solution and the ion exchange resin are separated by decantation, and left at room temperature (25 ° C.) for 1 hour to prepare a solution A2. On the other hand, PVA-105 (average degree of polymerization: 500, complete saponification type; saponification value: 98-99%) (manufactured by Kuraray);
90 g of water is added to 0 g, and the mixture is stirred at 90 ° C. for 5 hours to dissolve polyvinyl alcohol. (Hereinafter referred to as C1 solution.) Then, A2 solution: 80 g and C1 solution: 100
g, water: 112 g of the four solutions were mixed and mixed at room temperature (25
C) for 30 minutes to obtain a coating solution. This coating solution was coated once on one side of a mirror with an applicator, and heated and dried at 150 ° C. for 25 minutes in an oven (DK-400, manufactured by Yamato Scientific).
A transparent coating film (thickness: 8 μm) was obtained.

[0162]

Comparative Example 5 Zircosol ZN
Replacing zirconium oxychloride (made by Daiichi Kagaku Kagaku Kogyo) with A2 liquid and C1 liquid,
A4 where the four solutions of water and ethanol are mixed
A coating film is obtained by the same preparation method as in Example 1, except that four solutions of 60 g of solution, 100 g of C1 solution, 56 g of water and 56 g of ethanol are mixed.

[0163]

Comparative Example 6 When preparing liquid C1, PVA-105 (average degree of polymerization: 500, complete saponification type; saponification value: 98 to 9)
9%) (manufactured by Kuraray); 10 g, 90 g of water;
The mixture was stirred for 5 hours under the condition of ° C., and a solution obtained by dissolving polyvinyl alcohol was added to 40 g of a 25 wt% aqueous solution of polyacrylic acid (number average molecular weight: 300,000; manufactured by Wako Pure Chemical Industries), and 60 g of water was added. A coating film is obtained by the same preparation method as in Example 1 except that the solution obtained by stirring for 0.5 hour is used.

[0164]

Comparative Example 7 When preparing liquid C1, PVA-105 (average degree of polymerization: 500, partially saponified; saponification value: 98-99%) (manufactured by Kuraray) was used as polyvinyl alcohol.
A coating film is obtained by the same preparation method as in Example 1, except that VA-205 (average degree of polymerization: 500, complete saponification type; saponification value: 86.5 to 89.5%) (manufactured by Kuraray) is used.

[0165]

[Comparative Example 8] When preparing solution A2, 20 g of ion exchange resin WA-20 (manufactured by Mitsubishi Kasei) was mixed with solution A1, and the solution was stirred until the solution reached pH 2.0, and then ion exchanged with the solution. Separate the resin and decantation, room temperature (25 ° C)
For one hour and mixing four solutions of solution A2 and solution C1, water and ethanol, and then mixing three solutions of solution A2: 80 g, solution C1: 100 g, and water: 112 g. Same as Example 1 except for changing

[0166]

[Comparative Example 9] Zircosol Z was used to prepare A1 solution and A2 solution.
N (manufactured by Daiichi Kagaku Kagaku Kogyo); 98.5 g and water 147.
After adding 3 g and stirring for 5 minutes, the ion-exchange resin WA-
20 (manufactured by Mitsubishi Chemical);
After stirring to 4.0, the solution and the ion exchange resin were separated by decantation, and the separated solution was
Same as Example 1 except that it is used as A2 liquid.

[0167]

Comparative Example 10 Zircosol ZN (manufactured by Daiichi Kagaku Kagaku Kogyo Co., Ltd.); 98.5 g of water and 147.3 g of water were added, and the mixture was stirred for 5 minutes.
(Manufactured by Mitsubishi Kasei);
Then, the solution and the ion-exchange resin were separated by decantation, the separated solution was transferred to a sealed glass bottle, and the transferred solution was placed in a 95 ° C. oven (D
K-400, manufactured by Yamato Scientific Co., Ltd.) with a magnetic stirrer while stirring for 5 hours.
Same as Example 1 except that 0.13 g of 3% sodium hydroxide is added

[0168]

Comparative Example 11 A4 solution was mixed with four solutions of solution A2, solution C1, water and ethanol. Solution A2: 80 g and solution C1:
Four solutions of 100 g, 28 g of water, and 28 g of ethanol are mixed and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating solution, and a transparent coating film (film thickness: 12 μm) is obtained by the solution. Same as Example 1 except that

[0169]

Comparative Example 12 The process of preparing the A1 solution in Example 1 was performed by adding 98.5 g of zircosol ZN (manufactured by Daiichi Kagaku Kagaku Kogyo) and 147.3 g of water and stirring for 5 minutes. 20 (manufactured by Mitsubishi Kasei); 60 g was mixed therein, and the solution was stirred until the solution reached pH 3.0. Then, the solution and the ion exchange resin were separated by decantation, and the separated solution was transferred to a sealed glass bottle. Same as Example 1 except that the transferred solution was reacted in a 95 ° C. oven (DK-400, manufactured by Yamato Scientific Co., Ltd.) for 2 hours with stirring using a magnetic stirrer.

[0170]

Comparative Example 13 The process of preparing the solution A1 in Example 1 was carried out by adding 98.5 g of zircosol ZN (manufactured by Daiichi Kagaku Kagaku Kogyo) and 147.3 g of water and stirring for 5 minutes. 20 (manufactured by Mitsubishi Kasei); 60 g was mixed therein, and the solution was stirred until the solution reached pH 3.0. Then, the solution and the ion exchange resin were separated by decantation, and the separated solution was transferred to a sealed glass bottle. Same as Example 1 except that the transferred solution was reacted in a 95 ° C. oven (DK-400, manufactured by Yamato Scientific) using a magnetic stirrer while stirring for 20 hours.

[0171]

Comparative Example 14 Solution A2 of Example 1: 80 g and Solution C1: 1
In the process of mixing four solutions of 00 g, water: 56 g, and ethanol: 56 g, the A2 solution was brought to 60 g, and 30 g of alumina sol-520 (particle diameter: 10 to 20 nm, rod to granular, manufactured by Nissan Chemical Industries) was added. Same as Example 1 except that a mixing step was added

[0172]

[Comparative Example 15] In a heating and drying process at 150 ° C. for 25 minutes in an oven (DK-400, manufactured by Yamato Scientific Co., Ltd.), a far-infrared lamp was applied from the front side (painted surface) of a mirror to obtain a coating surface. Set the radiation thermometer (IT
-530S; manufactured by HORIBA, Ltd.).

[0173]

Comparative Example 16 In an oven (DK-400, manufactured by Yamato Scientific Co., Ltd.), an electric heater was applied from the back of a mirror to a heating and drying process at 150 ° C. for 25 minutes, so that the surface temperature of the coating reached 150 ° C. The same as in Example 19, except that the measurement was performed with a radiation thermometer (IT-530S; manufactured by HORIBA, Ltd.) for 5 minutes.

Table 1 shows Examples 1 to 32 and Comparative Examples 1 to 16.
2 shows a color difference (ΔE) measurement evaluation and an alkali resistance performance evaluation.

[0175]

[Table 1]

From Table 1, it can be seen that the pH of the coating solution was 2.5
With the above, addition of an inorganic oxide such as colloidal silica, and the use of a one-coat two-bake method as a heating and drying method, the color difference (ΔE) of the film can be reduced, and discoloration can be prevented. I understood. In addition, it was found that the addition of formaldehyde also improved the alkali resistance of the coating.

Table 2 shows Examples 1 to 32 and Comparative Examples 1 to 16.
Evaluation of acid resistance performance, anti-fogging performance, evaluation of appearance, evaluation of water resistance, and evaluation of cleanability are shown.

[0178]

[Table 2]

From Table 2, it was found that the addition of a catalyst or an yttrium salt to the composition and the immersion operation of the coating after the formation of the coating improved the antifogging performance. In addition, it was found that the appearance of the coating was improved by washing the substrate such as a ceria-containing liquid. In addition, it was found that the cleanability and appearance of the film differed depending on the value of [a] / [b1] of the composition, and that the film had optimum conditions for the value of [a] / [b1].

Table 3 shows Examples 1 to 32 and Comparative Examples 1 to 16.
3 shows the evaluation of the coating strength, the evaluation of the defoaming performance of bubbles in the coating liquid, the evaluation of the possibility of pipe corrosion by the coating liquid, the evaluation of the viscosity on the second day of the preparation of the coating liquid, and the evaluation of the adhesion by the cross-cut tape method.

[0181]

[Table 3]

From Table 3, [a] / [b1] of the above composition was obtained.
The strength of the film varies depending on the value of [a] / [a] /
It was found that there was an optimum condition for the value of [b1]. Also,
The amount of organic solvent added such as ethanol is indispensable for the defoaming effect of the coating solution, but depending on the amount added,
It was found that the viscosity increased and the stability of the liquid viscosity was lost. Therefore, as a countermeasure, it has been found that adding zirconium oxyacetate to the composition or zirconium compound is an effective method. It was also found that the cleaning of the substrate with a ceria-containing solution, the corona discharge surface treatment, and the adjustment of the pH of the coating solution were effective for the adhesion of the coating to the substrate.

[0183]

By preparing a water-absorbing coating composition by the method described above and applying it to a substrate to form a coating film, alkali resistance and acid resistance are high, and anti-fogging is achieved. It is possible to produce a composite material having good performance, dripping properties, appearance, and the like.

[Brief description of the drawings]

FIG. 1 is a configuration diagram of an apparatus for producing a moisture-absorbing film on a mirror using a flow coater.

[Explanation of symbols]

 1: Conveyor belt 2: Pretreatment steam cleaning device 3: Pure water cleaning device 4: Air knife device for draining 5: Flow coater 6: Indirect heating furnace 7: Main heating furnace 8: Post-processing steam spraying device A: Mirror B: Mirror or member advance method

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 3/36 C08K 3/36 4J038 5/07 5/07 5/098 5/098 5/56 5/56 7/18 7/18 C08L 29/04 C08L 29/04 A G02B 1/10 G02B 5/08 Z 5/08 1/10 Z F term (reference) 2H042 DA10 DA11 DA12 DB11 DE00 DE01 DE08 2K009 BB11 CC02 CC03 CC09 EE02 EE05 4D075 AC14 BB37Z BB49X BB65X BB79X CA02 CA34 CA39 CA40 DA03 DA06 DB13 DB31 EC10 4F100 AA02A AA17A AA20A AA27A AH08A AK01A AK21A AT00B BA02 DE01A EH46B EH462 EJ08B EJ082 EJ43B EJ55B EJ551 EJ64B EJ68B EJ681 EJ85B EJ852 GB07 GB08 GB32 GB90 JB01 JB05B JB07 JD15 JD15A JK14 JL06 JL08A JN01 JN01A JN01B YY00A 4J002 BE021 DE096 EE019 EG048 EZ006 FA086 FD016 FD207 GH00 HA08 4J038 CE021 HA156 HA216 HA306 JA31 JC38 KA04 KA06 KA08 NA01 NA04 NA06 NA07 PA01 PA07 PA 08 PA19 PB06 PB08

Claims (38)

[Claims] 1. A composition for absorbing the surface of a member to which it is applied, comprising: (a) a zirconium compound;
(B) a vinyl alcohol-containing water-absorbing organic polymer;
(A) [a] / [b1] which is a ratio of the molar concentration [a] of (a) to the molar concentration [b1] of the vinyl alcohol unit present in (b), which contains at least (c) a solvent. in the range of 0.2 to 0.4, comprising at least a zirconyl chelate and / or ZrO ₂ in (a) zirconium compounds, compositions. 2. The method according to claim 1, wherein [a] / [b1] is in the range of 0.25 to 0.5.
The composition of claim 1, wherein the composition is in the range of 32. 3. The composition according to claim 1, wherein the solvent is a water-containing organic solvent. 4. The composition according to claim 1, wherein the zirconyl chelate is zirconyl oxynitrate. 5. The composition according to claim 1, wherein the vinyl alcohol-containing water-absorbing organic polymer contains at least polyvinyl alcohol. 6. The composition according to claim 5, wherein the degree of saponification of the polyvinyl alcohol is 98% or more. 7. The composition has a pH of 2.5 or more,
The composition according to claim 1. 8. The composition according to claim 1, wherein the ZrO ₂ is formed from a zirconyl chelate. 9. The composition according to claim 1, further comprising a catalyst when the ZrO ₂ is produced from a zirconyl chelate. 10. The composition according to claim 9, wherein the catalyst is ammonia and / or hydrogen peroxide. 11. The composition according to claim 1, wherein when the ZrO ₂ is produced from a zirconyl chelate, the zirconyl chelate further comprises an yttrium salt and / or a magnesium salt. . 12. The composition according to claim 1, further comprising zirconium oxyacetate. 13. The composition according to claim 1, wherein when the ZrO ₂ is produced from a zirconyl chelate, the zirconyl chelate further comprises zirconium oxyacetate. 14. The composition according to claim 1, wherein the composition has an average particle size of 0.5 to 0.5.
Claim, characterized by having a ZrO ₂ of 40 nm 1 to 13
A composition according to any one of the preceding claims. 15. The composition according to claim 1, further comprising a fine inorganic oxide mixed with the composition. 16. The composition according to claim 15, wherein said inorganic oxide is silica. 17. The composition according to claim 1, wherein formaldehyde is further mixed into the composition. 18. The composition according to claim 1, which imparts anti-fogging property to the surface of the member to which the composition is applied. 19. On the surface of the member to which it is applied, water condensed water and / or water droplets adhering to the surface can be absorbed by the surface of the coating, whereby the surface condenses the moisture. 18. The composition according to any one of the preceding claims, wherein the composition is prevented from being clouded or overcast by water and / or water droplets. 20. The composition according to claim 1, which imparts dew-proofing to the surface of the member to which it is applied. 21. The method for preparing a composition according to claim 1, wherein the (a) zirconium compound is diluted with the (c) solvent when the composition is mixed. After the pH of the solution is adjusted to 2.5 or more,
A method for preparing a composition which produces ZrO ₂ or mixes with (b). 22. A method for producing a member having a hygroscopic surface, comprising applying the composition according to any one of claims 1 to 20 to the surface of the member and drying or curing the composition. A production method comprising: 23. The method according to claim 22, further comprising, before applying the composition according to claim 1 to the surface of the member, cleaning the surface of the member with a cleaning agent in advance.
The production method described in 1. 24. The cleaning agent is a ceria-containing liquid,
A method according to claim 23. 25. The method according to claim 22, comprising, prior to applying the composition according to any one of claims 1 to 20 to the surface of the member, preliminarily hydrophilizing the surface of the member. Method. 26. The method according to claim 25, wherein the hydrophilization is a corona discharge surface treatment. 27. The method according to claim 22, wherein the member is transparent and the resulting hygroscopic surface is also transparent. 28. A method of applying the composition according to any one of claims 1 to 20 to a member surface and drying or curing the composition, wherein the composition is applied to the member surface by curtain coating. 23. The method according to claim 22, comprising: 29. An operation of applying the composition according to any one of claims 1 to 20 to a surface of a member, and drying or curing the composition, comprising performing a one-coat two-bake method. The production method according to claim 22. 30. When applying the composition according to any one of claims 1 to 20 to a surface of a member and drying or curing the composition, a heat source is applied to the back surface of the member surface to which the composition is applied. 23. The method of claim 22, comprising placing on a side. 31. The method according to claim 30, wherein the heat source is a near infrared lamp. 32. The method according to claim 1, comprising applying the composition according to any one of claims 1 to 20 to a member surface, drying or curing the composition, and then immersing the composition. 22
The production method described in 1. 33. The method according to claim 3, wherein the immersion is steam cleaning.
3. The production method according to 2. 34. A member obtained by the method according to any one of claims 22 to 33, the surface of which is made hygroscopic. 35. The member according to claim 34, wherein said member is a mirror. 36. The member according to claim 34, wherein the member is a transparent plate-shaped member. 37. The member according to claim 34, wherein said member is a transparent lens. 38. The member according to claim 34, wherein the member is a transparent film.