JP2001040294A - Hygroscopic coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hygroscopic coating composition capable of obtaining coating film excellent in alkali resistance, acid resistance, antifog property, flow drop, appearance and cleaning property, useful for composite materials, etc., such as a side-mirror for automobile, etc. by including zirconyl, etc., a hygroscopic polymer and a solvent. SOLUTION: This composition changes surface of a substance such as a mirror, a transparent sheet material, a transparent lens, a transparent film, etc., into hygroscopic, comprises at least (A) one or more kinds selected from zirconyl such zirconium oxychloride, etc., zirconium nitrate, zirconium sulphate and zirconium halide such as zirconium chloride, etc., (B) a hygroscopic organic polymer such as polyvinyl alcohol, etc., and (C) water or an organic solvent including water. The composition preferably includes (D) a catalyst such as a hydrolysis catalyst, curing catalyst, etc., (E) a fluorine containing surfactant, (F) a heat absorbing agent, (G) a heat storage material, etc.

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 composite material having a hygroscopic property mainly used around water.

[0002]

2. Description of the Related Art With regard to mirrors used in water-filled spaces, for example, in mirrors placed in lavatories, it is often experienced that steam of hot water adheres to the surface and becomes cloudy and loses the visibility of reflected images. is there. As a cause, when steam adheres to the surface, it aggregates to form countless hemispherical water droplets,
Since the water drops diffusely reflect the light that enters, the visibility of the reflected image is lost. 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 water-absorbing film is provided to prevent generation of countless water droplets and to exhibit anti-fog performance. . The term "hygroscopicity" or "hygroscopicity" as used herein means, for example, that even when steam for hot water adheres to the mirror surface, the moisture of the steam is absorbed by the coating composition and does not remain on the surface. Say. As an example of a coating composition having this function, it is formed by hydrolyzing / polycondensing polyacrylic acid, one of water-absorbing polymers, finely divided silica, tetraethoxysilane, one of inorganic alkoxides, and the like. A water-absorbing coating composition or the like containing three components of a polymer having an OH group is considered.

[0003]

However, a mirror made of such a water-absorbent coating composition having a hygroscopic property has the following four problems. Such use as durable consumer goods has not yet been realized. The four problems are as follows. The first problem is that conventional water-absorbing coating compositions are susceptible to strong alkaline or strongly acidic chemicals, and are often used in places such as lavatories where household alkaline cleaning is frequently performed. Problems such as peeling off of the film due to adhesion occur. Second problem: In a humid place such as a bathroom,
When a mirror made of a water-absorbent coating composition having the above-mentioned hygroscopic property is provided, the coating is immediately saturated with moisture and loses the visibility of the reflection image. Therefore, even if this mirror is used in the bathroom, the surface is immediately clouded as in the case of a normal mirror, and there is no point in using it. Third problem: When a mirror made of the water-absorbing coating composition as described above is exposed to, for example, steam, the coating of the coating composition is saturated with moisture and the surface becomes cloudy, Generally, the surface is wiped with a cloth such as a towel to remove the fogging. However, there are problems such as fibers of the towel remaining in the coating and the coating being damaged. Fourth problem: A water-absorbing coating composition containing a polymer having an OH group formed by hydrolysis and polycondensation of an inorganic alkoxide as described above is liable to take in air bubbles during preparation or coating. Once the air bubbles are also taken in, they do not easily come off the coating agent, so there is a disadvantage that the film becomes a film containing the air bubbles. Among them, the fourth problem is solved by using a zirconyl binder reagent such as zirconium nitrate instead of a polymer having an OH group formed by hydrolysis and polycondensation of an inorganic alkoxide. In this case, there is a disadvantage that the coating is liable to be colored depending on the added amount.

[0004] In order to solve these problems, the applicant has made it possible for a hygroscopic film to have sufficient chemical resistance such as alkali resistance and acid resistance and cleaning properties, and to provide good water resistance and the like. With anti-fogging performance that delays the time until the film surface becomes cloudy, anti-fouling property that does not easily get dirty, dew-proofing property without water droplets
It is an object of the present invention to provide a composite material having a humidity control property capable of controlling the humidity of the atmosphere around the coating and a flow property capable of preventing adhesion of water droplets by forming a water film on the surface. By the way, the film having a cleaning property referred to herein means, for example, when the film of the water-absorbent coating composition having a hygroscopic property is saturated with moisture and the surface becomes cloudy, the surface may be wiped with a cloth such as a towel. This is a film that does not cause problems such as fibers of towels remaining in the film or damage to the film. Also, the water-resistant coating here is
For example, when the film of the water-absorbent coating composition having a hygroscopic property is saturated with moisture and the surface becomes cloudy, even if the surface is scratched with a hard object such as a nail, the problem that the film peels or is damaged. A film that does not occur. In addition, the alkali-resistant and acid-resistant coatings referred to here are, for example, even if a strong alkali chemical or a strong acid chemical adheres to the film of the water-absorbing coating composition having hygroscopicity, it takes a certain amount of time to adhere. If present, it refers to a coating that does not change the appearance or antifogging performance of the adhered portion.

[0005]

According to the first aspect of the present invention, there is provided a composition for absorbing moisture on a surface of a member to which the composition is applied, comprising zirconyl,
It is characterized by including at least one selected from zirconium nitrate, zirconium sulfate, and zirconium halide, a water-absorbing organic polymer, and a solvent.

In the present invention, zirconyl is used as the inorganic alkoxide which forms a polymer having an OH group by hydrolysis and polycondensation, and the alkoxide (hereinafter referred to as "alkoxide for hydrolysis") is converted into zirconyl to prepare a coating agent. Agglomeration and turbidity do not occur, and good results are obtained in terms of antifogging property and alkali resistance.

Further, in the present invention, zirconium nitrate is used as the alkoxide for hydrolysis, so that zirconium alkoxide, zirconyl, zirconium sulfate,
Not only the same effect as the effect of improving alkali resistance by mixing zirconium compounds such as zirconium nitrate and zirconium halide, but also the effect of eliminating aggregation and white turbidity during preparation of the coating agent can be obtained. In addition, the viscosity of the coating agent is lower than that of the zirconyl-containing coating agent, and there is also an effect that bubbles are less likely to enter. As a result, there is an advantage that handling at the time of coating is easy.

Further, in the present invention, by using zirconium sulfate as the alkoxide for hydrolysis, as in the case of zirconium nitrate, not only the effect of improving the alkali resistance due to the inclusion of the zirconium compound, but also the agglomeration during coating agent preparation, This has the effect of eliminating cloudiness and preventing air bubbles from entering. In particular, the point that bubbles are less likely to enter is more remarkable than zirconium nitrate. Therefore, there is an advantage that handling at the time of coating is easy.

In the present invention, the use of zirconium halide as the alkoxide for hydrolysis has the same effect as the alkali resistance improvement effect by mixing zirconium compounds such as zirconyl alkoxide, zirconyl, zirconium sulfate and zirconium halide. In addition, there is an effect that coagulation and white turbidity at the time of preparing the coating agent are eliminated. In addition, the viscosity of the coating agent is lower than that of the zirconyl-containing coating agent, and there is also an effect that bubbles are less likely to enter. Therefore, there is an advantage that handling at the time of coating is easy. Further, the hygroscopicity is further improved as compared with zirconium nitrate.

Claims made to solve the above problems
The invention according to claim 2, wherein the composition is the composition according to claim 1, wherein the solvent is water or a water-containing organic solvent. In the present invention, since the solvent is water or a water-containing organic solvent, compared to the case of using only the organic solvent, not only the alkali-resistant surface is improved, there is no change in viscosity, and a solution that does not contain bubbles can be formed. As a result, there is a particularly high effect in that there is no adverse effect on the appearance, such as air bubbles, in the film obtained by coating the member with the composition.

Claims made to solve the above problems
The invention according to claim 3, wherein the zirconyl is zirconium oxychloride. In the present invention, by converting zirconyl to zirconium oxychloride, good performance in alkali resistance and hygroscopicity can be obtained as described above, and compared with other zirconyl nitrates (also referred to as zirconium oxynitrate). Particularly good effects can be obtained in terms of hygroscopicity.

Claims made to solve the above problems
In the invention described in 4, the zirconium halide is zirconium chloride. In the present invention, among the above-mentioned zirconium halides, the use of zirconium chloride not only improves the alkali resistance, but also has a high effect in terms of moisture absorption compared to zirconium fluoride, which is another halogenated zirconium. .

Claims made to solve the above problems
The invention described in 5 is characterized in that the water-absorbing organic polymer contains at least polyvinyl alcohol. In the present invention, among the water-absorbing organic polymers, the use of polyvinyl alcohol provides an effect particularly high in alkali resistance as compared with polyacrylic acid, which is another water-absorbing organic polymer.

Claims made to solve the above problems
The invention according to claim 6 is characterized in that the composition according to any one of claims 1 to 5 further includes a catalyst. In the present invention, when a catalyst is contained, a composition is obtained which has not only an effect of improving alkali resistance due to mixing of a zirconium compound but also has a high hygroscopicity as compared with a composition containing no catalyst.

Claims made to solve the above problems
In the invention described in 7, the catalyst is a hydrolysis catalyst and / or
Or a curing catalyst. In the present invention, when the catalyst is a hydrolysis catalyst and a curing catalyst,
The hygroscopicity can be maintained considerably higher than other catalysts.

In the invention according to claim 8 which has been made to solve the above-mentioned problem, the composition according to claims 1 to 7 has the following features:
It is further characterized by containing an inorganic alkoxide and / or a polymer having an OH group formed by hydrolysis and polycondensation of the inorganic alkoxide. In the present invention,
Further, by containing at least one of the polymers, there is an effect of improving alkali resistance.

Claims made to solve the above problems
The invention described in Item 9 is characterized in that the composition according to any one of Claims 1 to 8, further comprises a fluorine-containing surfactant containing a hydrophilic group. In the present invention, the composition further contains a fluorine-based surfactant containing a hydrophilic group, so that the surface of the composite material coated with the surfactant is kept clean, and over a long period of time. The effect of maintaining good water absorption can be provided. That is, the antifouling property and the antifogging property can be improved.

According to a tenth aspect of the present invention, there is provided a composition according to the first to ninth aspects, further comprising a heat ray absorbing material. In the present invention, for example, if utilized for a transparent material such as glass, the heat ray absorbing material in the water-absorbing coating composition absorbs sunlight and the like, thereby suppressing an increase in indoor temperature due to radiation such as sunlight. While you can
The temperature of the glass surface can be increased to make it difficult for water droplets to adhere. That is, the antifogging property and the dewproofing property can be improved.

The invention according to claim 11 for solving the above-mentioned problem is characterized in that the composition according to claims 1 to 10 further contains a heat storage material. In the present invention, for example, if it is used for a transparent material such as glass, the heat storage material in the water-absorbing coating composition absorbs sunlight and the like, thereby suppressing an increase in indoor temperature due to radiation such as sunlight. At the same time, the temperature of the glass surface can be increased to make it difficult for water droplets to adhere. That is, the antifogging property and the dewproofing property can be improved.

The invention according to claim 12 which has been made to solve the above problem is characterized in that the composition according to any one of claims 1 to 11 further contains an ultraviolet absorber. In the present invention, for example, if it is used for a transparent material such as glass, it is possible to block short-wavelength sunlight harmful to the human body.

According to a thirteenth aspect of the present invention, there is provided a composition according to the first to twelfth aspects, further comprising an antibacterial metal or a compound thereof. In the present invention, the composition further contains an antibacterial metal or a compound thereof. For example, if the composition is used for a transparent material such as glass or a mirror, the generation and propagation of mold and bacteria on the surface of the composite material Can be prevented. That is, the appearance of the composite material can be maintained in a long and favorable state.

According to an embodiment of the present invention, there is provided a composition as set forth in any one of claims 1 to 13, further comprising photocatalyst particles, and a photocatalyst particle applied to the surface of the member to which the composition is applied. Is characterized by exhibiting hydrophilicity when irradiated. In the present invention, by further including photocatalyst particles, when the surface of the member to which the photocatalyst particles are applied (herein referred to as a coating) is irradiated with light, compared to the case where the photocatalyst particles are not added, only moisture absorption is achieved. In addition, even after the film is saturated with moisture, there is an effect that the maintainability of the surface of the film becomes hydrophilic.

In the invention according to claim 15 for solving the above-mentioned problem, the photocatalyst particles according to claim 14 are:
It is an anatase type titanium oxide. In the present invention, the photocatalytic particles are made of anatase-type titanium oxide, whereby the photocatalytic hydrophilicity of the composite material surface tends to be maintained for a long time, and the composite material having a particularly high hydrophilicity and hygroscopicity coating film Is obtained.

[0024] In the invention according to claim 16 which has been made to solve the above-mentioned problem, the composition according to any one of claims 1 to 15 is selected from the group consisting of Pt, Pd, Rh, Ru, Os and Ir. It is characterized by further comprising at least one metal. In the present invention, by further containing the metal, an effect such as a disinfectant that deprives bacteria and mold of the entire protoplasm can be provided. Thus, by adding these to the composite material, it is possible to prevent the generation and propagation of mold and bacteria on the surface of the composite material. Further, when added to the system to which the photocatalyst particles are added, the surface layer can enhance the redox activity of the photocatalyst, and can improve the decomposability of organic contaminants and the decomposability of harmful gases and odors.

According to a seventeenth aspect of the present invention, an antifogging property is imparted to a surface of a member to which the composition according to the first to sixteenth aspects is applied. .

According to the invention described in claim 18, which has been made to solve the above-mentioned problem, on the surface of a member to which the composition according to any one of claims 1 to 16 is applied, condensed water of moisture adhering to the surface and water And / or allowing water droplets to be absorbed by the surface of the coating, whereby the coating prevents the surface from being hazy or overcast by moisture condensate and / or water droplets.

According to a nineteenth aspect of the present invention, a contaminant attached to the surface of a member to which the composition of the first to sixteenth aspects is applied is easily removed by water. Characterized by being able to be washed away.

Claims made to solve the above problems
The invention described in Item 20 is characterized in that, on the surface of a member to which the composition according to any one of Claims 1 to 16 is applied, the surface of the member to which the composition is applied is provided with a dew-proof property.

Claims made to solve the above problems
The invention described in Item 21 is characterized in that, on the surface of a member to which the composition according to any one of Claims 1 to 16 is applied, moisture is imparted to the surface of the member to which the composition is applied.

Claims made to solve the above problems
The invention described in Item 22 is characterized in that it imparts drip properties to the surface of the member to which it is applied.

According to a twenty-third aspect of the present invention, a part or all of at least one kind selected from the first aspect is replaced with the first aspect. Wherein the solution is kept in an atmosphere of 50 ° C. or more for 1 hour or more, and then the solution is mixed with claim 1 (b). In the present invention,
By keeping the solution in an atmosphere of 50 ° C. or higher for 1 hour or more, the formed coating film has the effect of causing dropping properties and improving anti-fogging performance.

According to a twenty-fourth aspect of the present invention for solving the above-mentioned problem, a part or all of at least one kind selected from the first aspect is replaced with the first aspect. Wherein the solution is kept in an atmosphere of 90 ° C. or more for 1 hour or more, and then the solution is mixed with claim 1 (b). In the present invention,
Maintaining the solution in an atmosphere of 90 ° C. or higher for 1 hour or longer has the effect of improving alkali resistance.

According to a twenty-fifth aspect of the present invention, there is provided a composition according to the twenty-first aspect, wherein the composition according to the first to twenty-fourth aspects is maintained in an atmosphere at 50 ° C. or higher for 1 hour or more. In the present invention, this operation has the effect of improving the alkali resistance performance.

According to a twenty-sixth aspect of the present invention, a composition according to the first to twenty-fourth aspects is characterized in that the composition is maintained in an atmosphere at 90 ° C. or more for one hour or more. In the present invention, by performing this operation, not only the effect of improving the alkali resistance performance, but also,
This has the effect of improving the water resistance of the coating.

In the invention according to claim 27, which has been made to solve the above-mentioned problem, the composition according to any one of claims 23 to 26 has an average particle diameter of 0.1 nm to 10 nm.
It is characterized by having zirconia of 0 nm. In the present invention, by having zirconia as described above, a coating film having good cleaning properties as well as acid resistance and alkali resistance can be obtained.

In the invention according to claim 28, which has been made to solve the above-mentioned problem, the composition according to any one of claims 23 to 27 further comprises an average particle diameter of 5 nm to 2 nm.
It is characterized by mixing a 00 nm inorganic oxide. The inorganic oxide mentioned here is preferably an inorganic oxide such as silica, alumina, titania, and zirconia.
In the present invention, by performing such operations, a coating film having better antifogging property and alkali resistance can be obtained.

The invention according to claim 29, which has been made to solve the above-mentioned problem, is characterized in that silica is mixed as the inorganic oxide. In the present invention, by performing such an operation, a film having better antifogging property and alkali resistance can be obtained as compared with the case of using alumina sol or the like as another inorganic oxide.

The invention according to claim 30 for solving the above-mentioned problem is a method for preparing the composition according to any one of claims 1 to 22, 27, and 28, wherein A part or all of at least one kind selected from (a) is dissolved in the solvent according to claim 1 (c), and the solution is kept in an atmosphere at 50 ° C. or more for 1 hour or more. And claim 1 (b). In the present invention, by preparing the composition by the above-mentioned preparation method, there is an effect that the formed film has a dripping property and the antifogging performance is improved.

According to a thirty-first aspect of the present invention, there is provided a method for preparing a composition according to any one of the first to twenty-second, twenty-seventh, and twenty-eighth aspects. A part or all of at least one selected from (a) is dissolved in the solvent according to claim 1 (c), and the solution is kept in an atmosphere at 90 ° C. or more for 1 hour or more. And claim 1 (b). In the present invention, by preparing the composition by the above-described preparation method,
This has the effect of improving the alkali resistance performance.

In the invention according to claim 32, which has been made to solve the above-mentioned problem, the composition according to any one of claims 1 to 24 is kept in an atmosphere at 50 ° C. or more for 1 hour or more. A method for preparing a composition, comprising:
By performing such an operation in the present invention, there is an effect that the alkali resistance performance is improved.

In the invention according to claim 33, which has been made to solve the above-mentioned problem, the composition according to any one of claims 1 to 24 is kept in an atmosphere at 90 ° C. or more for 1 hour or more. A method for preparing a composition, comprising:
By performing such an operation in the present invention, not only the effect of improving the alkali resistance performance but also the effect of improving the water resistance of the coating film is obtained.

The invention according to claim 34, which has been made to solve the above-mentioned problem, is a method for making a surface of a member hygroscopic, wherein the composition is applied to the surface of the member, and the composition is dried or cured. A method comprising: In the present invention, by using the above-described method, for example, a member such as glass or plastic can be easily coated with the water-absorbing coating composition.

The invention according to claim 35, which has been made to solve the above-mentioned problem, includes cleaning the surface of the member with a cleaning agent before applying the composition according to the present invention to the surface of the member. It is characterized by becoming. In the present invention, by using the above-described method, it is possible to improve the appearance and shape without causing bubbles to enter the film after film formation.

According to a thirty-sixth aspect of the present invention for solving the above-mentioned problem, the cleaning agent is a ceria-containing solution. In the present invention, when the cleaning agent is a ceria-containing solution, the wettability of the substrate is improved, and a film can be formed without entrapping air bubbles between the substrate and the coating.

The invention according to claim 37, 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, by making the surface of the member hydrophilic in advance, the wettability of the substrate is improved, and the film can be formed without entrapping air bubbles between the substrate and the coating.

The invention according to claim 38, which has been made to solve the above-mentioned problem, is characterized in that the hydrophilization is irradiation with ultraviolet light having a wavelength of 260 nm or less. In the present invention, by irradiating the surface of the member with ultraviolet rays having a wavelength of 260 nm or less in advance, the wettability of the substrate is improved, and the film can be formed without entrapping bubbles between the substrate and the film. Also,
The effect is further improved by using it together with the cleaning by polishing ceria.

The invention according to claim 39, which has been made to solve the above-mentioned problem, is characterized in that the hydrophilization is a corona discharge treatment. In the present invention, by performing corona discharge treatment as the hydrophilicity, the wettability of the base material is improved, and the film can be formed without entrapping air bubbles between the base material and the coating film. Further, the effect is further enhanced by using the cleaning with ceria polishing together.

The invention according to claim 40, which has been made to solve the above-mentioned problem, is characterized in that the member is transparent and the obtained hygroscopic surface is also transparent.

The invention according to claim 41, which has been made to solve the above-mentioned problem, is to apply the composition to the surface of a member, and to dry or cure the composition, the composition must be 50 to 1%.
A production method comprising drying or curing at a first temperature of 50C, washing with water and / or an organic solvent, and then drying or curing at a second temperature of 60 to 200C. However, the second temperature is higher than the first temperature. In the present invention, by performing such an operation, for example, it is possible to solve the problem that a film generated when a water-absorbing coating composition is prepared using a reagent such as zirconium nitrate is colored brown. And a transparent film can be obtained.

The invention according to claim 42, which has been made to solve the above-mentioned problem, is characterized in that the surface is a member obtained by the above method, the surface of which is made hygroscopic.

The invention according to claim 43, which has been made to solve the above problem, is characterized in that the member is a mirror.

The invention according to claim 44, which has been made to solve the above problem, is characterized in that the member is a transparent plate member.

The invention described in claim 45 for solving the above-mentioned problem is characterized in that the member is a transparent lens.

The invention according to claim 46 for solving the above problem is characterized in that the member is a transparent film.

[0055]

DETAILED DESCRIPTION OF THE INVENTION Zirconium used in the present invention
The compound is zirconyl in the zirconium compound.
And zirconium nitrate, zirconium sulfate, halogenated
Zirconium is preferably used. Generally known
Some zirconium compounds have Z values whose oxidation number is difficult to identify.
rH_Two, ZrB, ZrC, ZrSi_Two, ZrN, ZrP,
ZrS_Two[Zr @ P] having an oxidation number of 0
(CH_Three)_Three｝ (Η⁶-toluene)_Two], [Zr (C₀)
_Two(Η ^Two-C_FiveH₆2), ZrCl having an oxidation number of 1 and oxidation number of 2
ZrX_Two(X = Cl, Br, I), ZrX having an oxidation number of 3
_Three(X = F, Cl, Br, I), etc., having an oxidation number of 4
Zircon, ZrSiO_FourAnd halogen
Zirconium zirconium_Four(X = F, Cl, Br,
I), ZrO_TwoSuch as zirconia, ZrOm (OH) n
(M = 4-n, integer of 4 ≧ n ≧ 0) zirconium oxoate
M, M4ZrO_Four, M_TwoZrO_Three(M = Na, K, 1 / 2C
a, 1 / 2Pb), zirconium nitrate,
Zirconium sulfate, zirconium hydroxide, [ZrF₆]
^2-, [ZrF₈]^Four-Zirconium fluoride such as fluoro
Complex, also represented by ZrO, commonly called zirconyl
+ Divalent atomic group zirconium oxychloride, oxywater
There are zirconium oxide, zirconium oxynitrate, etc.
Furthermore, Zr (OCH) obtained by hydrolysis / polycondensation reaction
_Three)_FourAnd zirconium alkoxides.

The zirconium compound has acid resistance among other inorganic compounds such as silicon, titanium and aluminum.
It is a compound that is said to have particularly good water resistance and alkali resistance. However, the hydrolysis / polycondensation reaction from an alkoxide or the like is considerably faster than other ones, and phenomena such as aggregation in a solvent are likely to occur, which is a difficult material to handle.

In the present invention, the inorganic alkoxide which forms a polymer having an OH group by hydrolysis and polycondensation and the alkoxide (hereinafter referred to as hydrolysis alkoxide) are converted into zirconyl, so that zirconyl can be prepared at the time of preparing the coating agent. Agglomeration and white turbidity did not occur, and in terms of anti-fogging property and alkali resistance, significantly better results were obtained as compared with the case of zirconium alkoxide. By the way, the reason that the zirconium alkoxide is easily aggregated is that the polycondensation reaction of the monomer obtained by hydrolysis of the zirconium alkoxide is quite fast, and the reaction proceeds before being mixed well when added to the water-absorbing polymer solution, It is considered that aggregation easily occurs. Further, the monomer obtained by hydrolysis of zirconium alkoxide has four alkoxyl groups per Zr,
Before the alkoxyl group is completely hydrolyzed, a polycondensation reaction of Zr-O-Zr is likely to occur, and the polymer is formed in a state where the alkoxyl group remains, and since the reaction becomes three-dimensional, aggregation tends to occur. Conceivable. On the other hand, zirconyl forms a complex with H ₂ O, OH ^- ions in an aqueous solution, and since there is an OH group from which a polycondensation reaction occurs from the beginning, the polycondensation reaction proceeds gently and aggregation does not easily occur. It is considered to be. Therefore, the surface of the zirconium compound having good alkali resistance and the surface capable of forming a uniform solution without aggregation are the causes of obtaining a composition having good alkali resistance and moisture absorption. Good or high hygroscopicity means that the time required for the coating surface to start to fog is long.

The zirconyl includes zirconium oxychloride, zirconium oxyhydroxide, zirconium oxynitrate, etc., each of which is ZrOCl ₂ , Zr
Although represented by chemical formulas such as O (OH) ₂ and ZrO (NO ₃ ) ₂ , there is no double bond such as Zr ＝ O, and -Zr
It is formed with a complicated structure such as forming a polymer chain of -O-Zr-. Therefore, the polymer of the inorganic portion of Zr is present from the beginning, and it is not necessary to carry out the above-described reaction of hydrolyzing to obtain an OH group, and the water-absorbing organic polymer and the inorganic portion of Zr are alternately bonded. And the polycondensation reaction proceeds gently. As a result, it is possible to form a film of the water-absorbing coating composition without having to worry about agglomeration and deterioration of antifogging performance.

Zirconium chloride has a continuous chain structure of [ZrCl ₆ ], and tends to easily become zirconium oxychloride. Therefore, this reagent has performance equivalent to zirconium oxychloride in terms of alkali resistance and the like. However, there are advantages in that the reaction between the inorganic portion of Zr and the water-absorbing organic polymer does not become disordered, and that the antifogging performance does not decrease.

Zirconium nitrate is expressed as Zr (NO ₃ ) ₂ , and in dry air, nitric acid is first released to change to zirconium oxynitrate. Therefore, ordinary commercial products exist in this state. by the way,
When this reagent is used by dissolving it in an ordinary organic solvent such as ethanol, the same alkali resistance as zirconium oxychloride can be obtained.However, it is easily hydrolyzed and polycondensed and does not exist stably. When added, the same problem as zirconium oxychloride occurs in that the viscosity increases and bubbles easily enter. However, when this is added to a nitric acid solution, zirconium oxynitrate is stably present as it is. Therefore, when this is added to a water-absorbing organic polymer solution, mixing can be performed without increasing the viscosity. Then, by adding a hydrolysis catalyst (for example, hydrochloric acid) other than nitric acid after mixing, the order can be changed to zirconium oxynitrate and zirconia to form a film without bubbles.

Further, zirconium sulfate is converted to Zr (SO
₄₎ In order to stably exist as a ₂ · 4H ₂ O, were dissolved in organic solvent, when added to the water-absorbing organic polymer solution, making compared to zirconium oxychloride coating composition was maintained antifogging also high Can be. Further, since the amount of acid is kept to a minimum as compared with zirconium nitrate, the increase in viscosity is suppressed to a low level, and a coating film free from bubbles and the like can be formed. And in the present invention,
By converting the alkoxide for hydrolysis to zirconium halide, zirconyl alkoxide or zirconyl,
Not only has the same effect as the effect of improving alkali resistance by mixing a zirconium compound such as zirconium sulfate or zirconium halide, but also has an effect of eliminating aggregation and white turbidity during preparation of a coating agent. In addition, the viscosity of the coating agent is lower than that of the zirconyl-containing coating agent, and there is also an effect that bubbles are less likely to enter. Therefore, there is an advantage that handling at the time of coating is easy. In addition, moisture absorption is also better than zirconium nitrate.

A zirconium compound used in the present invention,
Or, as zirconyl, in addition to the above reagents, zirconyl
Zirconium oxyacetate, one of conyl, oxysulfur
Zirconium oxide or Zr which is one of zirconium nitrate
(OH)_Two(NO_Three)_Two・ 4H_TwoO, ZrO (NO_Three)_Two, Zr_TwoO_Three
(NO_Three)_Two, Zr_FourO₇(NO_Three)_TwoEtc., zirconium acetate
And zirconium fluoride, zirconium bromide
, Zirconium iodide, zirconium oxychloride hydroxide
Water, zirconyl carbonate (zirconium oxycarbonate), water
Zirconyl oxide, zirconyl acetate, zirconium carbonate
Luammonium, zirconyl stearate, octyl
Zirconyl acid is preferably used. Furthermore, zirconi
Oxide compounds, oxyacid salts, organic acid salts or
Is a complex salt that is aqueous and stable in the processing solution.
Combined with at least one zirconium compound such as zirconyl
It is also possible to use them together. Specifically, ZrO
_Two, ZrO_Two・ XH_TwoO, M_TwoZrO_Three(Zirconic acid and
M) is an alkali metal, ZrO_Three・ 2H_TwoO, K_Four
ZrO_Four・ 2H_TwoO_Two・ 2H_TwoO (periodozirconium
Oxides and related compounds, such as ZrO (H_TwoP
O_Four)_Two, ZrP_TwoO ₇, Oxyacid salts such as ZrSiO4,
Zirconium halides such as roxy zirconium chloride,
Zirconium formate, zirconium acetate, dipropionate
Ruconium, zirconium caprylate, di-stearate
Organic acid zirconium salts such as ruconium, zirconium carbonate
Ammonium, sodium zirconium sulfate, diacetic acid
Ruconium ammonium, zirconium sodium oxalate
, Sodium zirconium citrate, zirconium citrate
Zirconium complex salts such as conium ammonium
It is.

As the water-absorbing organic polymer used in the present invention, polyvinyl alcohol, polyacrylic acids or polyalkylene oxide can be suitably used. The polyvinyl alcohol usually has an average degree of polymerization of 1,
500-1,500,000, preferably 3,500-
750,000 and a saponification value of 60 to 100%, preferably 70 to 90%. The polyacrylic acid is at least one selected from polyacrylic acid, polymethacrylic acid, and salts thereof. Examples of the polyalkylenoxide include polyethylene oxide, polypropylene glycol, and polypropylene oxide, and polyethylene oxide is particularly preferable. Usually, weight average molecular weight 30,000
~ 1,500,000, preferably 500,000 ~ 7
50,000 polyalkylene oxides are used.

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

Further, in addition to the water-absorbing organic polymer, 2
Hydroxyethyl methacrylate monomers, sepiolite, silica gel, dextran, alginic acid, sodium alginate, carrageenan, agarose, kaolin and the like can also be used. In the present invention, among the water-absorbing organic polymers, the use of polyvinyl alcohol has an effect of particularly high alkali resistance as compared with polyacrylic acid, which is another water-absorbing organic polymer. The following can be considered as a reason for this. It is considered that the reaction between the polyacrylic acid and the hydrolyzate of the zirconium compound forms an ester by dehydration condensation between the carboxylic acid of the polyacrylic acid and the OH group of the hydrolyzate of the zirconium compound. Therefore, when an alkali chemical such as sodium hydroxide comes into contact, hydrolysis catalyzed by the chemical occurs, and it is considered that the ester structure is destroyed.
On the other hand, it is considered that the reaction between polyvinyl alcohol and the hydrolyzate of the zirconium compound is caused by dehydration condensation between the OH group of the polyvinyl alcohol and the OH group of the hydrolyzate of the zirconium compound. Therefore, since the latter is less likely to be hydrolyzed than the former, it is considered that the alkali resistance is improved.

The solvent used in the present invention includes water or toluene, which is generally called an organic solvent,
An aromatic solvent such as xylene or an aliphatic solvent such as glycerin is used, and particularly, an organic solvent compatible with water such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and butyl alcohol is preferable. is there. This organic solvent is often used with water. The amount of the solvent used is preferably an alkoxide,
100 to 500 parts by weight based on 100 parts by weight of the total of the polymer having an OH group, the water-absorbing organic polymer and the curing catalyst
0 parts by weight, more preferably about 3000 parts by weight.

In the water-absorbing coating composition of the present invention, for example, zirconium chloride, which is one of the zirconium halides, is hydrolyzed by the action of a hydrolysis catalyst, and changes to zirconyl such as zirconium oxychloride. Then, a halogen such as chlorine in zirconium oxychloride is further hydrolyzed to be converted to an OH group. Thus, the zirconium compound is converted into a monomer having an OH group. This change also occurs for zirconium nitrate, zirconium sulfate, and the like. Further, deprotonation of the OH group occurs, and as a result, the hydrolyzate starts polycondensation to form a polymer or oligomer having an OH group in the molecule. At the same time, the OH group portion of the water-absorbing organic polymer present in the composition reacts with the hydrolyzed zirconium compound or the polymer or oligomer having an OH group to form an inorganic portion of Zr and an organic polymer derived from the water-absorbing organic polymer. A composite polymer having a moiety is formed. When the respective components of the composition are mixed, the hydrolysis reaction and the polycondensation reaction partially proceed as described above. Therefore, a zirconium compound, a hydrolyzate thereof, a polycondensation oligomer or polymer of the hydrolyzate, a water-absorbing organic compound, It is a colloidal sol in which a polymer, a hydrolyzate derived from the zirconium compound and a polycondensation or cross-linking reaction product of the water-absorbing organic polymer are mixed. This becomes the water-absorbing coating composition.

As the catalyst used in the present invention, a hydrolysis catalyst and a curing catalyst are preferably used. The hydrolysis catalyst is used for a hydrolysis reaction of an inorganic alkoxide. Therefore, when a polymer having an OH group (which may be a relatively low molecular weight oligomer) in which the inorganic alkoxide is previously hydrolyzed to some extent and polycondensed is used,
A hydrolysis catalyst may not be required.

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. Further, inorganic bases such as sodium hydroxide, potassium hydroxide, and ammonia are also used as catalysts. These hydrolysis catalysts, 0.01 to 0.5 parts by weight based on 100 parts by weight of the alkoxide,
It is preferably 0.015 to 0.3 parts by weight. 0.01
If the amount is less than 0.5 parts by weight, the hydrolysis may be insufficient. If the amount exceeds 0.5 parts by weight, the polycondensation reaction may proceed and the viscosity may increase.

The curing catalyst is mainly used as a catalyst for a polycondensation reaction of a hydrolyzate of an alkoxide or a zirconium compound, and as a catalyst for a crosslinking reaction of a water-absorbing organic polymer. , A zirconium compound, and a water-absorbing organic polymer as a catalyst for a polycondensation reaction and / or a cross-linking reaction. 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. Examples of the quaternary phosphonium salt include tetrabis (hydroxymethyl) phosphonium chloride and tetrabutylphosphonium bromide.

As the organic amine, ethylamine,
Examples include dimethylamine, N, N-dimethylamine, tributylamine, tri-n-propylamine, tripentylamine, tripropargylamine, N, N, N-trimethylethylenediamine, n-hexylamine and the like.

The amino acids include glycine and the like.

The metal acetylacetonate includes:
Examples include aluminum acetylacetonate, indium acetylacetonate, chromium acetylacetonate, titanium acetylacetonate, and cobalt acetylacetonate.

As the metal acetylacetonate, aluminum acetylacetonate is preferably used.

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

The Lewis acids include stannic chloride, aluminum chloride, ferric chloride, titanium chloride, zinc chloride, antimony chloride and the like.

Examples of the peroxide include hydrogen peroxide.

Examples of the perchloric oxide include lithium perchlorate.

The oxo acids and salts thereof include, in addition to the peroxides and perchloric oxides, orthoboric acid, metaboric acid, trimetaboric acid, hypoboric acid, carbonic acid, cyanic acid, isocyanic acid, thunderic acid , Orthosilicic acid, metasilicic acid, peroxonitrate, nitrous acid, peroxonitrite, nitroxylic acid, hyponitrite, phosphoric acid, diphosphoric acid, pyrophosphoric acid, triphosphoric acid, polyphosphoric acid, 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 to be used is preferably a total amount of the alkoxide, the polymer having an OH group, and the water-absorbing organic polymer in the water-absorbing coating composition.
The amount is 0.01 to 2 parts by weight, more preferably 0.05 part by weight, based on 00 parts by weight. If the amount is more than 2 parts by weight, the polycondensation proceeds rapidly, so that it is difficult to dissolve in the organic solvent, and the resulting coating becomes non-uniform, so that the strength may be reduced.

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

When M is Si, the alkoxide is
It is represented by Si (OR1) ₄ . Here, R1 is preferably a lower alkyl group having 1 to 4 carbon atoms. Such alkoxysilanes include Si (OCH ₃ ) ₄ , Si (OC
₂ H ₅ ) _{4 and the} like.

When M is Al, the alkoxide is
It is represented by Al (OR2) ₃ . Here, R2 is preferably a lower alkyl group. Such aluminum alkoxides include Al (OCH ₃ ) ₄ and Al (OC
_{2 H 5) 3, Al (} O-n-C 3 H 7) 3, Al (O-iso-
C ₃ H ₇ ) ₃ and Al (OC ₄ H ₉ ) ₃ . The aluminum alkoxide may be used as a mixture of two or more kinds. Such aluminum alkoxides
Usually, it is used by mixing with the alkoxysilane, and by using aluminum alkoxide, the light transmittance and heat resistance of the obtained coating film are improved. The amount of the aluminum alkoxide to be used is preferably in the range of 10 parts by weight or less, more preferably about 5 parts by weight, based on 100 parts by weight of the alkoxysilane. If the amount is more than 10 parts by weight, the formed polymer tends to gel, and the resulting coating film may be cracked.

When M is Ti, the alkoxide is represented by Ti (OR 3) ₄ . Here, R3 is preferably a lower alkyl group. Such titanium _{alkoxide, Ti (O-CH 3)} 4, Ti (O-C
_{2 H 5) 4, Ti (} O-n-C 3 H 7) 4, Ti (O-iso
—C ₃ H ₇ ) ₄ and Ti (O—C ₄ H ₉ ) ₄ . The titanium alkoxides may be used as a mixture of two or more kinds. Such a titanium alkoxide is usually used as a mixture with the alkoxysilane,
By using the titanium alkoxide, the UV resistance of the obtained coating film is improved, and the heat resistance of the substrate is also significantly improved. The amount of the titanium alkoxide to be used is within a range of 3 parts by weight or less, preferably about 1 part by weight, based on 100 parts by weight of the alkoxysilane. Three
When the amount is more than the weight part, the formed polymer becomes brittle, and the coating film is easily peeled when the base material is coated.

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

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

In the present invention, an inorganic alkoxide is hydrolyzed by the action of a hydrolysis catalyst, and an alkoxy group and a halogen (X) are changed to an OH group. Furthermore, the OH group is deprotonated by the action of the curing catalyst, and as a result, the hydrolyzate starts polycondensation to form a polymer or oligomer having an OH group in the molecule. At the same time, by a curing catalyst or the like, the OH group portion of the water-absorbing organic polymer present in the composition reacts with the hydrolyzed alkoxide or the polymer or oligomer having an OH group,
(1) A composite polymer having an inorganic portion such as Si represented by M in the formula and an organic portion derived from a water-absorbing organic polymer is formed. In addition, when a zirconium compound is added and the respective components of the composition are mixed, the hydrolysis reaction and the polycondensation reaction partially proceed as described above, so that the inorganic alkoxide, its hydrolyzate, and the weight of the hydrolyzate are mixed. Condensation oligomers or polymers, zirconium compounds, hydrolysates, polycondensation oligomers or polymers of the hydrolysates,
The water-absorbing organic polymer, the hydrolyzate derived from the alkoxide, the hydrolyzate derived from the zirconium compound, and the polycondensation or cross-linking reaction product of the water-absorbing organic polymer are mixed to form a colloidal sol. (1) When X in the formula has a specific functional group, the functional group may further react. For example, when X is a group having an epoxy group, the epoxy group is opened by a base catalyst to generate an OH group, and the reaction with an alkoxide or a water-absorbing organic polymer proceeds. When X is a group having a vinyl group, a reactive monomer can be bonded to the vinyl group. When a coating composition containing such an inorganic alkoxide and a coating composition containing only a zirconium compound whose inorganic portion is not the same are applied to each substrate, and dried, and then heat-treated at 80 ° C. or more, the above-mentioned intermediate condensation reaction And the crosslinking reaction proceeds,
A composite polymer having a three-dimensional structure is formed. This polymer is a polymer having an inorganic part and an organic part. That is, since this polymer has an insoluble skeleton which is an inorganic portion, a film formed by this polymer is insoluble in water and an organic solvent and has high surface hardness. Furthermore, since this polymer has a water-absorbing organic polymer that is an organic portion, a hydrophilic portion derived from the water-absorbing organic polymer is present on the surface of the formed film, and moisture is adsorbed to that portion. Further, when a carbonyl group, a carboxyl group, an amino group, a vinyl group, an amino group, an epoxy group, or the like is present at the terminal of the group (1) of formula X, moisture is further adsorbed to the group.

In the present invention, the composition further contains at least one of an inorganic alkoxide and a polymer having an OH group formed by hydrolysis and polycondensation, whereby zirconium is added. In addition to the effect of improving the alkali resistance due to the mixing of the compound, there is an effect that aggregation and white turbidity during coating agent preparation are eliminated. In addition, the viscosity of the coating agent is lower than that of the zirconyl-containing coating agent, and there is also an effect that bubbles are less likely to enter. Therefore, there is an advantage that handling at the time of coating is easy. For this reason, for example, Si (OC
When an alkoxysilane such as H ₃ ) ₄ is added by hydrolysis and polycondensation, the speed of hydrolysis and polycondensation is considerably slower than that of a zirconium compound. This has the effect of reducing the speed of polycondensation with the water-absorbing polymer. Therefore, it is considered that a liquid which hardly causes aggregation and which is easy to handle at the time of coating is formed.

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 the amount exceeds 0.5 parts by weight, the hardness of a film formed by the obtained composition 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, trifluoropropyltrichlorosilane, trifluoropropylbromosilane, trifluoropropyl Propyltrimethoxysilane, trifluoropropyltriethoxysilane, heptadecafluorooctyltrimethoxysilane, heptadecafluorooctyltriethoxysilane, and the like can be suitably used.

In the present invention, by further adding a fluorine-containing surfactant containing a hydrophilic group,
The effect of keeping the surface of the composite material coated thereon clean and maintaining good water absorption over a long period of time can be given. That is, the antifouling property and the antifogging property can be improved. This is because the water-repellent / oil-repellent portion derived from the fluorine-based surfactant and the hydrophilic portion derived from the water-absorbing coating composition microscopically disperse the surface of the composite material, so that lipophilicity and This is because any hydrophobic or hydrophilic contaminants hardly adhere to the surface, and even if they adhere, the adhesion is unstable and easily comes off.

In the present invention, a heat ray absorbing material may be further contained in the water absorbing coating composition. If the heat absorbing material is used for a transparent material such as glass, the room temperature due to radiation such as sunlight can be reduced. 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.

In the present invention, if it is used for a transparent material such as glass, for example, the heat storage material in the water-absorbing coating composition absorbs sunlight and the like, thereby increasing the indoor temperature due to radiation of the sunlight and the like. Can be suppressed, and the temperature of the glass surface can be increased to make it difficult for water droplets to adhere. That is, the antifogging property and the dewproofing property can be improved.

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 antibacterial 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 for forming the surface layer of the member may be formed by dispersing silicone or silica for forming an inorganic skeleton, a zirconium compound, or zirconia and photocatalyst particles. 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 water-absorbent coating composition has a three-dimensional skeleton structure having an inorganic portion and an organic portion, and incorporates an organic polymer having water absorbency and photocatalytic particles for photocatalytically hydrophilic in the gaps. , Fixed by the adhesive strength of the skeleton. The water-absorbing organic polymer contained in the three-dimensional skeleton has high water absorption, and when fine water droplets such as steam come in contact with the surface of the member, without dew condensation on the surface of the water, the water-absorbing coating in the water-absorbing coating The water-absorbing organic polymer reaches and is absorbed. In addition, when the photocatalytic composition also included in the three-dimensional skeleton is highly hydrophilized by being induced by the added photocatalyst, hydrophobic contaminants and charged floating substances adhere to the outermost surface of the member. It is difficult to adhere, and even if it adheres, the adhesion is unstable, and the oxidative decomposition action of the photocatalyst is added, so that the adhered substance is easily decomposed and desorbed. Such an effect is called a self-cleaning effect.
Therefore, the composite material coated with the water-absorbing coating composition can have both performances. That is, a composite material having the hygroscopic property of the water-absorbing organic polymer and the hydrophilic property of the photocatalyst particles can be obtained.

The following photocatalyst particles can be used. When the photocatalyst particles are anatase-type titanium oxide, rutile-type titanium oxide, zinc oxide, or strontium titanate, the light to be irradiated may be sunlight, indoor lighting, a fluorescent lamp, a mercury lamp, an incandescent lamp, a xenon lamp, or a high-pressure lamp. Light from a 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, The illuminance of the excitation light is preferably 0.001 mW / cm ² or more, more preferably 0.01 mW / cm ^2.
cm ² or more, most preferably 0.1 mW / cm ²
That is all.

Further, according to a preferred embodiment of the present invention, it is preferable to add a metal such as Ag, Cu and 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 the antifouling property.

According to another preferred embodiment of the present invention,
In the photocatalytic coating composition layer, Pt, Pd, Ru,
A platinum group metal such as Rh, Ir, Os can be added. The surface layer to which such a metal is added can enhance the redox activity of the photocatalyst, and can improve the decomposability of organic contaminants and the decomposability of harmful gases and odors.

In the present invention, there is provided a member whose surface is coated with a transparent water-absorbing coating composition comprising a composite polymer having an inorganic skeleton crosslinked with an organic molecule. The water-absorbing coating composition is composed of an inorganic polymer and an organic polymer which are cross-linked and bonded 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, humidity control property, and dropping property.

The anti-fogging property referred to herein is, for example, in the case of a mirror,
When small water droplets such as steam come into contact with the film surface of the member, without dew condensation on the surface, the water reaches the water-absorbing organic polymer in the water-absorbing coating composition forming the surface layer, and is absorbed. It means that fogging can be prevented and the visibility of the reflected image can be maintained.

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. This is a phenomenon in which 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 is damaged even when washed with detergent etc. Means

The term “humidity control” as used herein means that the surface layer of the substrate is
It has the following functions. Its function is that, for example, when a composite material in which a mirror with a heater is coated with the composition is prepared and installed in a room, if the surrounding humidity is high, the humidity becomes constant. Until the film absorbs moisture in the atmosphere, the humidity can be reduced. In addition, when the humidity is low, when the heater is turned on, the film becomes difficult to absorb moisture, so that the surrounding humidity is not reduced. Thus, it refers to such a function as adjusting the humidity by operating the heater. When the water-absorbing coating composition as described above is formed into a film,
This is possible because the absorption and release of water can be repeated reversibly. Ultimately, humidity control means having the function of keeping the humidity around the member constant.

[0107] The term "dropping property" as used herein refers to a phenomenon in which a water film without irregular reflection of light is generated on the surface of the film after the film absorbs moisture and is saturated, thereby maintaining the transparency of the film. Usually, after the film absorbs moisture and saturates, water droplets are generated on the film, and the water droplets cause irregular reflection of light, thereby causing a phenomenon that the film becomes cloudy. However, a film having a drip property suppresses generation of water droplets by forming a water film, and maintains transparency of the film.
Therefore, when dripping properties occur, the antifogging property can be maintained as long as there is a water film, so even in an environment such as a bathroom where the film is easily saturated at high humidity, by using this film, A water film is generated, and the antifogging performance can be maintained for a long time. This coating is effective when used, for example, in bathroom mirrors.

In the present invention, the above-mentioned claim 1 is provided.
A part or all of at least one selected from (a) is dissolved in the solvent of claim 1 (c), and the solution is kept in an atmosphere of 50 ° C. or more for 1 hour or more, and then the solution is dissolved. By mixing with the above-mentioned claim 1 (b), the formed film has more drip property than in the case where the above-mentioned method is not performed, and the anti-fog performance can be improved. In this case, the reaction conditions of the temperature and time for holding the aqueous solution such as zirconyl necessary to generate droplets in the formed film, the type of the solute or solvent such as zirconyl, or
It depends on the concentration of the solute in the solution. For example, taking a 2% aqueous solution of zirconium oxychloride as an example,
Dropping property is generated by a combination of a mixture of polyvinyl alcohol and a mixture which is left standing or stirred for 16 hours in an atmosphere of 95 ° C. In addition, in the case of this ethanol solution, dropping property is generated by a combination of a solution which is left standing or stirred with stirring in an atmosphere at 50 ° C. for 1 hour and polyvinyl alcohol. Furthermore, taking an aqueous solution of zirconium oxychloride having a concentration of 10% as an example, a combination of a solution left at rest in an atmosphere at 95 ° C. for 48 hours and polyvinyl alcohol generates droplets. By the way, when the solution is allowed to stand in a high-temperature atmosphere for a long time, a phenomenon that the solution becomes cloudy occurs. This is the result of the formation of insoluble zirconia crystals, but the use of such a result is not practical because the transparency of the coating film is lost. Therefore, it is desirable to use each solute at a temperature and for a time within a range in which the clouding does not occur. For these reasons, it is desirable that the solute is left in an atmosphere of at least 50 ° C. for one hour before use. In the case of a 2% aqueous solution of zirconium oxychloride, more preferably,
It is desirable to use it after leaving it to stand in an atmosphere of 95 ° C. for 16 to 35 hours. By the way, when heating, one or more hydrolysis catalysts such as nitric acid and / or a curing catalyst such as hydrogen peroxide may be added and reacted. The catalyst is not limited to those described above.

In the present invention, the above-mentioned claim 1 is provided.
A part or all of at least one selected from (a) is dissolved in the solvent of claim 1 (c), and the solution is kept in an atmosphere at 90 ° C. or more for 1 hour or more, and then the solution is dissolved. By mixing the above and claim 1 (b), the alkali resistance can be improved as compared with the case where the above is not performed. In this case, the reaction conditions of the temperature and time for allowing the aqueous solution of zirconyl or the like necessary to bring about an improvement in alkali resistance performance to the formed film are the same as the conditions for improving the dropping property, such as zirconyl or the like. Of the solute and the solvent, or the concentration of the solute in the solution. For this reason, in the case of a 2% aqueous solution of zirconium oxychloride, the temperature is preferably 1 to 38 in an atmosphere at 95 ° C.
It is desirable to use it after standing for a long time. More preferably, it is desirable to use after leaving still in an atmosphere of 95 ° C. for 26 to 30 hours. Most preferably, 100
It is desirable to leave it in an atmosphere of ° C for at least 17 hours or to use it after reflux. By the way, when heating, one or more hydrolysis catalysts such as nitric acid and / or a curing catalyst such as hydrogen peroxide may be added and reacted. Also,
In the present invention, maintaining the composition in an atmosphere at 50 ° C. or higher for 1 hour or longer has the effect of improving alkali resistance. The effect of improving the alkali resistance has an effect of being further improved by combining with the invention described in claim 30 or 31. For example,
A 2% aqueous solution of zirconium oxychloride is allowed to stand in an atmosphere at 95 ° C. for 30 hours, and then mixed with a water-absorbing organic polymer such as polyvinyl alcohol.
After standing for 1 hour in an atmosphere at 0 ° C., the composition is applied to a substrate, whereby a film having higher alkali resistance can be formed as compared with the composition left standing in an atmosphere at 25 ° C. for 1 hour. Preferably, the reaction conditions are such that the composition is allowed to stand in an atmosphere at 50 ° C. for 10 hours or more before use. More preferably, in an atmosphere of 50 ° C., 3
It is desirable to use it after leaving it for 0 hours or more.

In the present invention, the composition is
By holding in an atmosphere of 0 ° C or more for 1 hour or more,
In addition to the effect of improving the alkali resistance, there is the effect of improving the water resistance of the coating. For example, a 2% strength aqueous solution of zirconium oxychloride is placed in an atmosphere at 95 ° C.
After allowing to stand for 30 hours, the mixture is mixed with a water-absorbing organic polymer such as polyvinyl alcohol, and the composition is allowed to stand in an atmosphere of 90 ° C. for 1 hour, and applied to a substrate, whereby the composition is heated to 25 ° C. A film having higher alkali resistance and higher water resistance than a film left standing for 1 hour in the atmosphere described above can be obtained. As the reaction conditions, it is preferable that the composition is left to stand in an atmosphere of 90 ° C. for 17 hours or more before use. More preferably, in an atmosphere of 95 ° C., 1
It is desirable to use it after standing still for 7 hours or more. As described above, the zirconyl aqueous solution or the like, by maintaining a mixture with a water-absorbing organic polymer or the like at a high temperature, dripability, alkali resistance, as a reason for improving the water resistance, by performing the above operation, Zirconyl such as zirconium oxychloride turns into zirconia, which acts as a crosslinking agent for water-absorbing organic polymers such as polyvinyl alcohol,
This is presumably because cross-linking between the polymers is performed to obtain a film having a high bonding force. Zirconia is much more water- and alkali-resistant than inorganic oxides such as silica.
It is a substance with strong acid resistance. Therefore, by using a small amount of this crosslinking agent, the water resistance, alkali resistance, and acid resistance of the coating can be improved with a small amount as compared with other crosslinking agents such as silicate hydrolyzate. Therefore, the use of this cross-linking agent is considered to cause a phenomenon such as dripping since the reduction of the water absorption capacity due to the decrease in the number of binding sites caused by the cross-linking of the water-absorbing organic polymer is minimized. Can be Further, the reaction conditions of the temperature and time for holding the aqueous solution such as zirconyl necessary to generate droplets in the formed film, the type of the solute or solvent such as zirconyl, or
Different phenomena are observed depending on the concentration of the solute in the solution.The reason for this is considered to be that, due to these factors, the rate of formation of zirconia crystals and the average particle size of the zirconia generated from the solute such as zirconyl greatly differ. Can be For example, taking an aqueous solution of zirconium oxychloride having a concentration of 10% as an example, when it is boiled, the boiling time is 1% at 40 hours, 20% at 60 hours, 80% at 80 hours, and 100% at 100 hours. This is the zirconia generation rate. The generation rate of zirconia referred to here means that zirconium oxychloride is 1
If it is set to 00, it is the ratio changed to zirconia. The rate of formation depends on the concentration of zirconium oxychloride. In the case of 4%, the boiling rate is 1 hour for 20 hours.
%, 20% at 30 hours, 80% at 40 hours, and 100% at 60 hours. Thus, the lower the concentration, the sooner it changes to zirconia. Further, this tendency tends to be further accelerated by the addition of a catalyst such as ammonia or hydrogen peroxide. Further, the particle size of zirconia or the manner of growth of the particle size also depends on the zirconium oxychloride concentration, and the smaller the concentration, the smaller the particle size tends to be. From these, the type of the solute or solvent such as zirconyl, or a solution in which the concentration of the solute in the solution is adjusted, by applying an optimal reaction time and temperature, the amount and particle size of the zirconia generated, By adjusting the water resistance, alkali resistance, and acid resistance of the coating film, and adjusting the flow resistance so that droplets can be generated, and reacting with the water-absorbing organic polymer, a coating agent having the above-described properties is prepared. be able to.

The average particle size of zirconia in the composition is preferably in the range of 0.1 nm to 100 nm. More preferably, the range is 0.5 nm to 4 nm. If the average particle size is lower than 0.1 nm, the appearance during film formation will be poor, and for example, when zirconium nitrate or the like is used, it will be easy to color. In addition, zirconia having an average particle diameter exceeding 100 nm is a cause of deteriorating the transparency of the formed coating film. Incidentally, the zirconia in the composition is derived from zirconyl such as zirconium nitrate, and long-time heating at 50 ° C. or more or 90 ° C. or more in an aqueous solution of this material can increase its particle size. . However, 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. For example, a 20% by weight aqueous solution of zirconium nitrate has a concentration of 1 to 4N, and as it is, the reaction from zirconium nitrate to zirconia hardly proceeds due to excess nitrate ions and hydrogen ions, and the particle size hardly grows. Further, even if it grows, a coating agent using it can form only a film having a problem in cleanability and the like. However, if nitrate ions are removed in advance with an anion exchange resin, the reaction proceeds promptly and the particle size grows, and a coating agent using this can form a coating having no problem in terms of cleanability and the like. And the optimum pH depends on the solid concentration,
pH 1.8 to pH 3 are preferable, and pH is more preferable.
2 to 2.5. This pH adjustment also has the effect of removing the disadvantage of the coating becoming brown when using zirconium nitrate. However, if the pH is too high, the viscosity of the coating agent will increase, making it difficult to handle. The anion exchange resin used at this time is not particularly limited as long as it can exchange anions such as nitrate ions. And the functional groups of the ion exchange resin are also amine-based such as dimethylethanolamine and trimethylamine,
Quaternary ammonium and the like can be used. The shape of the obtained zirconia may be any of a granular shape and a chain shape, and is not particularly limited. Further, a hydrolysis catalyst such as nitric acid and / or a curing catalyst such as hydrogen peroxide may be added to grow the particle size of zirconia. 50 ° C or higher or 90 ° C in an aqueous solution of a material such as zirconium nitrate
Even when heating is not performed for a long time as described above, pH 1.8 to pH 3
By adjusting the pH as described above, the average particle diameter of zirconia in the composition can be changed to a target size in the range of 0.1 nm to 100 nm. And a good coating of In addition, at this time, even if a hydrolysis catalyst such as nitric acid and / or a curing catalyst such as hydrogen peroxide is added instead of heating, the particle size of zirconia can be grown, so that the cleaning property is good. Such a method is also preferable for obtaining a coating.

The amount of zirconium and / or zirconyl and zirconia used is preferably 1 to 100 parts by weight of the total of zirconium and / or zirconyl and zirconia, the water-absorbing organic polymer and the curing catalyst.
90 parts by weight, more preferably 10 to 80 parts by weight. Most preferably, it is 30 to 70 parts by weight. As the inorganic oxide, oxides such as yttrium oxide, niobium oxide, and cerium oxide are preferable in addition to titania, silica, alumina, and zirconia.

The 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. Further, as the shape, a chain shape is more preferable than a granular shape since a chain shape is better in terms of antifogging performance.

The amount of the inorganic oxide used is zirconium and / or zirconyl and zirconia, inorganic oxide,
1 to 70 parts by weight, more preferably 10 parts by weight, based on 100 parts by weight of the total of the water-absorbing organic polymer and the curing catalyst.
６０60 parts by weight. Most preferably, it is 30 to 50 parts by weight. Examples of the 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 average particle diameter is less than 5 nm, the stability of the dispersed state is poor, and if it is more than 200 nm, the transparency of the resulting coating film is poor.

The substrate of the member is not particularly limited, and may be, for example, metal, ceramics, glass, plastic, wood,
Stone, cement, concrete, fiber, fabric, combinations thereof, and laminates thereof 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 provided with a reflection coat on the back surface, a plastic, glass, and a reflection coat provided on the surface of a base material such as a metal. Mirror, plastic, glass, metal, etc. provided with a reflective coat on the surface of the base material, and further provided with a transparent hard coat, a mirror made of a mirror polished metal base, a mirror made of a mirror polished metal base A mirror provided with a transparent hard coat on the surface thereof, a mirror provided with a transparent hard coat on a transparent plastic substrate provided with a reflective coat on the back surface, and the like can be suitably used. As the transparent plate member as the member, a plastic member such as polyethylene terephthalate, polyvinyl chloride, and methacrylic resin, and a plate glass such as soda-lime glass, borosilicate glass, and aluminosilicate glass can be suitably used. As the transparent lens as the member, a plastic member such as polyethylene terephthalate, polyvinyl chloride, or methacrylic resin, or a glass such as soda-lime glass, borosilicate glass, or aluminosilicate glass can be suitably used. The transparent film as the member,
Plastic members 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, whereby the abrasion resistance and the weather resistance can be improved and the reflected light can be reduced.
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.

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 liquid. Next, this coating liquid is applied to at least one surface of the base material, and is heated at a temperature of 80 ° C. or higher, preferably 120 ° C.
The coated substrate of the present invention can be obtained by heating and drying at a temperature in the range of -200 ° C. If necessary, the heat treatment may be performed after the coating liquid is applied several times.

The coating method is not particularly limited, and any coating method such as a bar coating, a die coating, a curtain flow coating, and a roll coating can be used.

When the composition is applied to the member surface and the composition is dried or cured, the composition is heated to 50 to 150 ° C.
In the invention of drying or curing at the first temperature of the above, further washing with water and / or an organic solvent, and then drying or curing at the second temperature of 60 to 200 ° C., by performing such an operation, for example, In addition, it is possible to solve the problem that a film generated when a water absorbing coating composition is prepared using a reagent such as zirconium nitrate is colored brown, and a transparent film can be obtained. In the present invention, as the organic solvent, an aromatic solvent such as toluene and xylene, which are generally referred to as an organic solvent, and an aliphatic solvent such as glycerin are used.
Organic solvents that are compatible with water, such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and butyl alcohol, are preferred. This organic solvent is often used with water. Further, the first temperature is a composition that does not flow out with water and does not color,
There is no particular limitation, and preferably 50 to 10
At 0 ° C, more preferably 80 to 100 ° C. The second 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, more preferably 130 to 180 ° C. 150 ° C. Further, the method of washing with water and / or an organic solvent is not particularly limited as long as a sufficient washing effect can be obtained. For example, water is directly discharged onto the surface of the composition by a tube hose. I can deal with that.

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. Further, 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 coating the surface of the substrate with the water-absorbing coating composition, the surface of the substrate is washed in advance with a detergent to remove impurities on the surface of the substrate and to improve the hydrophilicity of the substrate. Can be enhanced. As a result, there is no air bubble between the substrate and the coating, and a coating with high adhesion is obtained, and the alkali resistance of the coating is improved.

The term “washing” as used herein refers to degreasing cleaning for removing foreign substances adhering to the 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, increasing the smoothness of the substrate surface, and lowering the surface tension. 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 to make a detergent by dissolving particles mainly composed of ceria in a neutral detergent, etc.
By washing the surface of the base material, the surface of the base material can be degreased or smoothed, and the hydrophilicity can be improved by reducing the surface tension.

In the present invention, as described above, by pre-hydrophilizing, the wettability of the substrate is improved, and a clean film can be formed, and the bonding force between the substrate and the film is increased. High coatings are obtained.

For the above-mentioned hydrophilization, chemicals, ultraviolet rays, radiation,
Oxidation of the substrate surface by discharge or the like is considered as a technique. Among them, in particular, when irradiating the substrate with an ultraviolet lamp of 260 nm or less, and then applying a coating liquid, ceria polishing is performed. When used together, the hydrophilicity of the substrate is further enhanced as compared with the case alone, and a clean film can be formed, and a film having high alkali resistance can be obtained. In addition, among the above-mentioned hydrophilic treatments, when the coating liquid is applied after the substrate is subjected to corona discharge treatment, the hydrophilicity of the substrate becomes higher than that in the case of irradiation with an ultraviolet lamp, and a clean film can be formed, and the alkali resistance is improved. A high-performance coating can be obtained.
Particularly effective when used in combination with ceria polishing.

This is because, by corona discharge on the surface of the base material, high-speed and low-speed electrons in the air gap collide with oxygen atoms to generate excited oxygen molecules. To change. The active species can oxidize the surface of the base material and improve the wettability of the coating liquid. In this way, by modifying the surface of the base material, the adhesion between the base material and the coating composition, which is another polar molecule, can be promoted, and as a result, the alkali resistance can be improved. .

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, considering the water absorption capacity of the anti-fog mirror of the present invention, very large water droplets do not adhere, but the steam of hot water adheres to the surface and is easily clouded, so that it can be suitably used in a washroom.

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,
Examples of the transparent film as the member include wrapping paper for food, an automobile side mirror, an automobile room mirror,
It can be used as an anti-fog film to be attached to a mirror installed in a bathroom or a washroom. In addition, the member is suitable for any of a ceiling material for a bathroom having antifouling property and anti-dew property, a pipe for a toilet, a pipe for water supply, a urinal, a toilet, a trap for a toilet, a wash bowl, and a wash trap. Available to 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 floor boards, 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 cocks, toothbrush stands, lavatory 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.

[0128]

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. Alkali resistance performance evaluation method 1; Pipe Uniche (manufactured by Unicharm) was dropped on the surface of the membrane with a disposable 3 ml disposable dropper for 1.5 hours at 25 ° C. for 0.5 hour or 1 hour.
After standing for 2 hours, flush with water and examine the state after that part. ；: 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 breath is blown, but the trace remains. X; When the breath is blown on the trace, it becomes cloudy and the trace remains. Alkali resistance performance evaluation method 2: 3 m hight (made by Kao)
(1) The solution is dropped on the surface of the membrane with a disposable dropper, allowed to stand for 1 hour in an atmosphere at 25 ° C., and then 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 breath is blown, but the trace remains. X; When the breath is blown on the trace, it becomes cloudy and the trace remains. Acid resistance performance evaluation method: 3 m of sun paul (kincho)
(1) The solution is dropped on the surface of the membrane with a disposable dropper, allowed to stand for 1 hour in an atmosphere at 25 ° C., and then 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. X; When the breath is blown on the trace, it becomes cloudy and the trace remains.

Antifogging performance evaluation method: A sample having a coating film is placed in an atmosphere of 25 ° C. and 100% humidity, and the time required for fogging 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. Flow; a time in which the time required for clouding is 1 minute and 30 seconds or more, in which the dropping property is developed. 2: Time until clouding is 2 minutes or more. A: Time until fogging is less than 2 minutes, 1 minute 30 seconds or more. ；: The time until fogging is from 1 minute to 1 minute 30 seconds. Δ: Time until clouding is 30 seconds or more and 1 minute or less. ×: Time until clouding is 30 seconds or less.

Evaluation of appearance A: No air bubbles, turbidity or coloration is observed on the film surface. ；: A film in which air bubbles, turbidity, and coloring are only slightly observed on the film surface. Δ: Some bubbles, cloudiness, and coloring are observed on the film surface. X: Air bubbles, turbidity, and coloring are considerably conspicuous on the film surface.

Evaluation of Water Resistance After the substrate coated with the coating was immersed in water at room temperature for 30 seconds, the surface of the coating was scratched with nails and dried, and the scratching marks were observed and evaluated. A: No scar is seen on the film surface. ；: No scar is seen on the film surface, but a dent is seen in the film immediately after scratching with the nail. However, those that cannot be seen when dried. Δ: No scar is seen on the film surface, but a dent is seen in the film immediately after scratching with the nail. In addition, those in which the depression of the coating does not heal even after drying. ×: A scar is seen on the film surface.

Evaluation of Cleanability After the coated substrate was immersed in water at room temperature for 30 seconds, the surface of the film was wiped with a jersey cotton cloth, and the wiped marks were observed and evaluated. ；: 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. Average particle size measurement of zirconia particles

A part or all of at least one selected from the above (a) is dissolved in the solvent of the above (c), and the solution is kept in an atmosphere of 50 ° C. or 90 ° C. or more for 1 hour or more. The average particle diameter of zirconia in a zirconia solution (for example, a 95 ° C. heat treatment solution of zirconium nitrate) obtained by the above method is measured with a dynamic light scattering photometer DLS.
-600 (manufactured by Otsuka Electronics Co., Ltd.). The obtained value is the average particle size of zirconia in the coating composition.

[0134]

Example 1 Zirconium oxychloride octahydrate (manufactured by Wako Pure Chemical Industries, Ltd.);
Stirred for minutes. On the other hand, polyvinyl alcohol 3,500
Partially saponified type; Saponification value: 86 to 90% (manufactured by Wako Pure Chemical Industries);
After stirring for an hour, the polyvinyl alcohol was dissolved. Then, the two solutions were mixed and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating liquid. Apply this coating solution to one side of the mirror
The coating was repeated and heated and dried at 150 ° C. for 20 minutes to obtain a transparent coating film (film thickness: 2 μm).

[0135]

Example 2 0.8 g of a zirconyl nitrate dihydrate (manufactured by Wako Pure Chemical Industries, Ltd.), a 2N aqueous solution of nitric acid; 0.05 g and 15.2 g of methanol were added and stirred for 5 minutes. On the other hand, polyvinyl alcohol 3,500 partially saponified type; saponification value: 86-
90% (manufactured by Wako Pure Chemical Industries);
The mixture was stirred at 0 ° C. for 5 hours to dissolve the polyvinyl alcohol. Then, the two solutions were mixed, 0.01 g of a 35% hydrochloric acid solution was further added, and the mixture was stirred at normal temperature (25 ° C.) for 30 minutes to obtain a coating liquid. This coating solution was applied once on one side of a mirror and heated and dried at 150 ° C. for 20 minutes to obtain a transparent coating film (film thickness: 2 μm).

[0136]

Example 3 Zirconium sulfate (manufactured by Aldridge);
0.8 g and 35% hydrochloric acid aqueous solution; 0.05 g and methanol 1
5.2 g was added and stirred for 5 minutes. On the other hand, polyvinyl alcohol 3,500 partially saponified type; saponification value: 86-9
0% (manufactured by Wako Pure Chemical Industries);
The mixture was stirred at a temperature of 5 ° C. for 5 hours to dissolve the polyvinyl alcohol. Then, the two solutions are mixed and mixed at room temperature (2
(5 ° C.) for 30 minutes to obtain a coating solution. This coating solution was applied once on one side of a mirror and heated and dried at 150 ° C. for 20 minutes to obtain a transparent coating film (film thickness: 2 μm).

[0137]

Example 4 A coating film (film thickness: 2 μm) was obtained in the same manner as in Example 3, except that zirconium sulfate was changed to zirconium chloride (manufactured by Aldridge).

[0138]

Example 5 First, 0.01 g of N, N-dimethylbenzylamine (manufactured by Wako Pure Chemical); 0.99 g of methanol
And stirred for 5 minutes. Then, this solution was further added to the same coating liquid as in Example 1, and the mixture was stirred at room temperature for 10 minutes to obtain this coating liquid. Then, this coating solution is applied once on one side of the mirror once,
After heating and drying at 20 ° C for 20 minutes, the coating film (film thickness: 2
μm) was obtained.

[0139]

Example 6 0.3 g of ethyl silicate 40 (manufactured by Colcoat), 0.05 g of a 2% aqueous nitric acid solution and 2.7 g of methanol were added, and the mixture was stirred for 12 hours to carry out hydrolysis. (Ethyl silicate hydrolyzed solution) Then, 0.6 g of zirconium oxychloride octahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and 11.4 g of methanol were added to this solution, followed by stirring for 5 minutes. On the other hand, polyvinyl alcohol 3,500 partially saponified type; saponification value: 86 to 90% (manufactured by Wako Pure Chemical Industries);
90 g of water was added to 0 g, and the mixture was stirred at 90 ° C. for 5 hours to dissolve polyvinyl alcohol. Then, the two solutions are mixed and stirred at room temperature (25 ° C.) for 30 minutes.
A coating liquid was obtained. This coating solution was applied once on one side of a mirror and heated and dried at 150 ° C. for 20 minutes to obtain a transparent coating film (film thickness: 2 μm).

[0140]

Example 7 A coating film (film thickness: 2 μm) was obtained in the same manner as in Example 3 except that zirconium sulfate was changed to zirconium fluoride (manufactured by Aldridge).

[0141]

Example 8 0.4 g of zirconium oxychloride octahydrate (manufactured by Wako Pure Chemical Industries) and 19.6 g of water were added and stirred for 5 minutes. Then, it is left still for 1 hour in an oven (DK-400, manufactured by Yamato Scientific) at 50 ° C. On the other hand, polyvinyl alcohol PVA217, degree of polymerization: 1,700, saponification value:
86-90% (manufactured by Kuraray); 7 g, water; 93 g,
The mixture was stirred at 90 ° C. for 5 hours to dissolve the polyvinyl alcohol. Then, the two solutions were mixed and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating liquid. This coating solution was applied once on one side of a mirror, and heated and dried at 150 ° C. for 20 minutes to obtain a transparent coating film (film thickness: 2 μm).
m) was obtained.

[0142]

Example 9 0.4 g of zirconium oxychloride octahydrate (manufactured by Wako Pure Chemical Industries) and 19.6 g of water were added and stirred for 5 minutes. Then, it is left still in an oven at 90 ° C. (DK-400, manufactured by Yamato Scientific) for 1 hour. On the other hand, polyvinyl alcohol PVA217, degree of polymerization: 1,700, saponification value:
86-90% (manufactured by Kuraray); 7 g, water; 93 g,
The mixture was stirred at 90 ° C. for 5 hours to dissolve the polyvinyl alcohol. Then, the two solutions were mixed and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating liquid. This coating solution was applied once on one side of a mirror, and heated and dried at 150 ° C. for 20 minutes to obtain a transparent coating film (film thickness: 2 μm).
m) was obtained.

[0143]

EXAMPLE 10 0.4 g of zirconium oxychloride octahydrate (manufactured by Wako Pure Chemical Industries) and 19.6 g of water were added and stirred for 5 minutes. Then, it is left still for 30 hours in a 90 ° C. oven (DK-400, manufactured by Yamato Scientific). On the other hand, polyvinyl alcohol PVA217, degree of polymerization: 1,700, saponification value: 86 to 90% (manufactured by Kuraray); water; 93 g to 7 g, and stirred at 90 ° C. for 5 hours to dissolve the polyvinyl alcohol Was. Then, mix these two solutions,
The mixture was stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating liquid. This coating solution is applied once on one side of the mirror once,
After heating and drying for 0 minutes, a transparent coating film (film thickness: 2
μm) was obtained.

[0144]

Example 11 0.4 g of zirconium oxychloride octahydrate (manufactured by Wako Pure Chemical Industries) and 19.6 g of water were added and stirred for 5 minutes. Then, it is left still for 30 hours in a 90 ° C. oven (DK-400, manufactured by Yamato Scientific). On the other hand, polyvinyl alcohol PVA217, degree of polymerization: 1,700, saponification value: 86 to 90% (manufactured by Kuraray); water; 93 g to 7 g, and stirred at 90 ° C. for 5 hours to dissolve the polyvinyl alcohol Was. Then, mix these two solutions,
Stir at room temperature (25 ° C) for 30 minutes, and heat at 50 ° C in an oven (D
(K-400, manufactured by Yamato Scientific Co., Ltd.) for 1 hour. The coating solution thus obtained is applied once on one side of the mirror by applying once.
After heating and drying at 50 ° C. for 20 minutes, a transparent coating film (film thickness: 2 μm) was obtained.

[0145]

Example 12 0.4 g of zirconium oxychloride octahydrate (manufactured by Wako Pure Chemical Industries) and 19.6 g of water were added and stirred for 5 minutes. Then, it is left still for 30 hours in a 90 ° C. oven (DK-400, manufactured by Yamato Scientific). On the other hand, polyvinyl alcohol PVA217, degree of polymerization: 1,700, saponification value: 86 to 90% (manufactured by Kuraray); water; 93 g to 7 g, and stirred at 90 ° C. for 5 hours to dissolve the polyvinyl alcohol Was. Then, mix these two solutions,
The mixture is stirred at a normal temperature of 50 ° C. (25 ° C.) for 30 minutes, and left standing in a 90 ° C. oven (DK-400, manufactured by Yamato Scientific) for 1 hour. The coating liquid thus obtained was applied once on one surface of a mirror, and was applied and heated and dried at 150 ° C. for 20 minutes. As a result, a transparent coating film (film thickness: 2 μm) was obtained.

[0146]

Example 13 0.4 g of zirconium oxychloride octahydrate (manufactured by Wako Pure Chemical Industries) and 19.6 g of water were added and stirred for 5 minutes. Then, it is left still for 30 hours in a 90 ° C. oven (DK-400, manufactured by Yamato Scientific). On the other hand, polyvinyl alcohol PVA217, degree of polymerization: 1,700, saponification value: 86 to 90% (manufactured by Kuraray); water; 93 g to 7 g, and stirred at 90 ° C. for 5 hours to dissolve the polyvinyl alcohol Was. Then, mix these two solutions,
The mixture is stirred at 50 ° C. and room temperature (25 ° C.) for 30 minutes, and left standing in a 90 ° C. oven (DK-400, manufactured by Yamato Scientific) for 17 hours. The coating liquid thus obtained was applied once on one surface of a mirror, and was applied and heated and dried at 150 ° C. for 20 minutes. As a result, a transparent coating film (film thickness: 2 μm) was obtained.

[0147]

Example 14 0.4 g of zirconium oxychloride octahydrate (manufactured by Wako Pure Chemical Industries) and 19.6 g of water were added and stirred for 5 minutes. Then, it is left still for 30 hours in a 90 ° C. oven (DK-400, manufactured by Yamato Scientific). On the other hand, polyvinyl alcohol PVA217, degree of polymerization: 1,700, saponification value: 86 to 90% (manufactured by Kuraray); water; 93 g to 7 g, and stirred at 90 ° C. for 5 hours to dissolve the polyvinyl alcohol Was. Then, mix these two solutions,
The mixture is stirred at 50 ° C. and room temperature (25 ° C.) for 30 minutes, and left standing in a 90 ° C. oven (DK-400, manufactured by Yamato Scientific) for 17 hours. 0.4 g of water and 3.6 of zirconium oxychloride octahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) were added to the solution thus obtained.
g was added and the solution obtained by stirring for 5 minutes was added to obtain a coating solution. This coating solution was applied once on one side of a mirror and heated and dried at 150 ° C. for 20 minutes to obtain a transparent coating film (film thickness: 2 μm).

[0148]

Example 15 10 g of zirconium nitrate dihydrate (manufactured by Wako Pure Chemical Industries) and 40 g of water were added, followed by stirring for 5 minutes. Then, ion exchange resin WA-20 (manufactured by Mitsubishi Kasei); 30 g
And stir until the solution is at pH 3.0.
Thereafter, the solution and the ion exchange resin were separated by decantation, and the separated solution was placed in an oven (DK-
400, manufactured by Yamato Scientific Co., Ltd.) for 5 hours. further,
Leave at room temperature (25 ° C.) for 24 hours. On the other hand, polyvinyl alcohol PVA235, degree of polymerization: 3,500, saponification value: 86-90% (manufactured by Kuraray); water; 45 g were added to 5 g, and the mixture was stirred at 90 ° C. for 5 hours to dissolve the polyvinyl alcohol. Was. And these two solutions and 100g
Of water and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating liquid. This coating solution was applied once on one side of a mirror, applied and heated and dried at 90 ° C. for 13 minutes, then washed by flowing water on the coating surface for 5 minutes, and further heated and dried at 150 ° C. for 10 minutes. However, a transparent coating film (thickness: 10 μm) was obtained.

[0149]

Example 16 10 g of zirconium nitrate dihydrate (manufactured by Wako Pure Chemical Industries) and 40 g of water were added and stirred for 5 minutes. Then, ion exchange resin WA-20 (manufactured by Mitsubishi Kasei); 30 g
And stir until the solution is at pH 3.0.
Thereafter, the solution and the ion exchange resin were separated by decantation, and the separated solution was placed in an oven (DK-
400, manufactured by Yamato Scientific Co., Ltd.) for 10 hours. Furthermore, it is left at room temperature (25 ° C.) for 24 hours. On the other hand, polyvinyl alcohol PVA235, degree of polymerization: 3,500, saponification value: 86 to 90% (manufactured by Kuraray);
Was added and stirred at 90 ° C. for 5 hours to dissolve the polyvinyl alcohol. And these two solutions and 10
0 g of water was mixed and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating liquid. This coating solution was applied once on one side of a mirror, applied and heated and dried at 90 ° C. for 13 minutes, then washed by flowing water on the coating surface for 5 minutes, and further heated and dried at 150 ° C. for 10 minutes. However, a transparent coating film (thickness: 10 μm)
was gotten.

[0150]

Example 17 10 g of zirconium nitrate dihydrate (manufactured by Wako Pure Chemical Industries) and 40 g of water were added and stirred for 5 minutes. Then, ion exchange resin WA-20 (manufactured by Mitsubishi Kasei); 30 g
And stir until the solution is at pH 3.0.
Thereafter, the solution and the ion exchange resin were separated by decantation, and the separated solution was placed in an oven (DK-
400, manufactured by Yamato Scientific Co., Ltd.) for 15 hours. Furthermore, it is left at room temperature (25 ° C.) for 24 hours. On the other hand, polyvinyl alcohol PVA235, degree of polymerization: 3,500, saponification value: 86 to 90% (manufactured by Kuraray);
Was added and stirred at 90 ° C. for 5 hours to dissolve the polyvinyl alcohol. And these two solutions and 10
0 g of water was mixed and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating liquid. This coating solution was applied once on one side of a mirror, applied and heated and dried at 90 ° C. for 13 minutes, then washed by flowing water on the coating surface for 5 minutes, and further heated and dried at 150 ° C. for 10 minutes. However, a transparent coating film (thickness: 10 μm)
was gotten.

[0151]

Example 18 10 g of zirconium nitrate dihydrate (manufactured by Wako Pure Chemical Industries) and 40 g of water were added and stirred for 5 minutes. Then, ion exchange resin WA-20 (manufactured by Mitsubishi Kasei); 30 g
And stir until the solution is at pH 3.0.
Thereafter, the solution and the ion exchange resin were separated by decantation, and the separated solution was placed in an oven (DK-
400, manufactured by Yamato Scientific Co., Ltd.) for 17 hours. Furthermore, it is left at room temperature (25 ° C.) for 24 hours. On the other hand, polyvinyl alcohol PVA235, degree of polymerization: 3,500, saponification value: 86 to 90% (manufactured by Kuraray);
Was added and stirred at 90 ° C. for 5 hours to dissolve the polyvinyl alcohol. And these two solutions and 10
0 g of water was mixed and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating liquid. This coating solution was applied once on one side of a mirror, applied and heated and dried at 90 ° C. for 13 minutes, then washed by flowing water on the coating surface for 5 minutes, and further heated and dried at 150 ° C. for 10 minutes. However, a transparent coating film (thickness: 10 μm)
was gotten.

[0152]

Example 19 10 g of zirconium nitrate dihydrate (manufactured by Wako Pure Chemical Industries) and 40 g of water were added and stirred for 5 minutes. Then, ion exchange resin WA-20 (manufactured by Mitsubishi Kasei); 30 g
And stir until the solution is at pH 3.0.
Thereafter, the solution and the ion exchange resin were separated by decantation, and the separated solution was placed in an oven (DK-
400, manufactured by Yamato Scientific Co., Ltd.) for 21 hours. Furthermore, it is left at room temperature (25 ° C.) for 24 hours. On the other hand, polyvinyl alcohol PVA235, degree of polymerization: 3,500, saponification value: 86 to 90% (manufactured by Kuraray);
Was added and stirred at 90 ° C. for 5 hours to dissolve the polyvinyl alcohol. And these two solutions and 10
0 g of water was mixed and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating liquid. This coating solution was applied once on one side of a mirror, applied and heated and dried at 90 ° C. for 13 minutes, then washed by flowing water on the coating surface for 5 minutes, and further heated and dried at 150 ° C. for 10 minutes. However, a transparent coating film (thickness: 10 μm)
was gotten.

[0153]

Example 20 10 g of zirconium nitrate dihydrate (manufactured by Wako Pure Chemical Industries) and 40 g of water were added and stirred for 5 minutes. Then, ion exchange resin WA-20 (manufactured by Mitsubishi Kasei); 30 g
And stir until the solution is at pH 3.0.
Thereafter, the solution and the ion-exchange resin are separated by decantation and allowed to stand at room temperature (25 ° C.) for 24 hours. on the other hand,
Polyvinyl alcohol PVA235, degree of polymerization: 3,50
0, saponification value: 86-90% (manufactured by Kuraray); 5 g of water;
45 g was added, and the mixture was stirred at 90 ° C. for 5 hours to dissolve polyvinyl alcohol. Then, the two solutions and 100 g of water were mixed and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating liquid. This coating solution is applied once on one side of a mirror, heated and dried at 90 ° C. for 13 minutes, and then washed by flowing water on the coating surface for 5 minutes.
After heating and drying for 10 minutes, a transparent coating film (film thickness: 10
μm) was obtained.

[0154]

Example 21 10 g of zirconium nitrate dihydrate (manufactured by Wako Pure Chemical Industries) and 40 g of water were added and stirred for 5 minutes. Then, ion exchange resin WA-20 (manufactured by Mitsubishi Kasei); 30 g
And stir until the solution is at pH 3.0.
Thereafter, the solution and the ion exchange resin were separated by decantation, and the separated solution was placed in an oven (DK-
400, manufactured by Yamato Scientific Co., Ltd.) for 15 hours. Furthermore, it is left at room temperature (25 ° C.) for 24 hours. On the other hand, polyvinyl alcohol PVA235, degree of polymerization: 3,500, saponification value: 86 to 90% (manufactured by Kuraray);
Was added and stirred at 90 ° C. for 5 hours to dissolve the polyvinyl alcohol. And these two solutions and 10
0 g of water and colloidal silica Snowtex OUP
(Particle size; 40-100, chain, manufactured by Nissan Chemical Industries) 20
g was mixed and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating liquid. This coating solution is applied once on one side of the mirror,
After heating and drying at 90 ° C for 13 minutes, 5
After washing for 10 minutes and further heating and drying at 150 ° C. for 10 minutes, a transparent coating film (film thickness: 10 μm) was obtained.

[0155]

EXAMPLE 22 10 g of zirconium nitrate dihydrate (manufactured by Wako Pure Chemical Industries) and 40 g of water were added and stirred for 5 minutes. Then, ion exchange resin WA-20 (manufactured by Mitsubishi Kasei); 30 g
And stir until the solution is at pH 3.0.
Thereafter, the solution and the ion exchange resin were separated by decantation, and the separated solution was placed in an oven (DK-
400, manufactured by Yamato Scientific Co., Ltd.) for 15 hours. Furthermore, it is left at room temperature (25 ° C.) for 24 hours. On the other hand, polyvinyl alcohol PVA235, degree of polymerization: 3,500, saponification value: 86 to 90% (manufactured by Kuraray);
Was added and stirred at 90 ° C. for 5 hours to dissolve the polyvinyl alcohol. And these two solutions and 10
0 g water and colloidal silica Snowtex ZL
(Particle size; 70-100, granular, manufactured by Nissan Chemical Industries) 20
g was mixed and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating liquid. This coating solution is applied once on one side of the mirror,
After heating and drying at 90 ° C for 13 minutes, 5
After washing for 10 minutes and heating and drying at 150 ° C. for 10 minutes, a transparent coating film (film thickness: 10 μm) was obtained.

[0156]

Example 23 10 g of zirconium nitrate dihydrate (manufactured by Wako Pure Chemical Industries) and 40 g of water were added and stirred for 5 minutes. Then, ion exchange resin WA-20 (manufactured by Mitsubishi Kasei); 30 g
And stir until the solution is at pH 3.0.
Thereafter, the solution and the ion exchange resin were separated by decantation, and the separated solution was placed in an oven (DK-
400, manufactured by Yamato Scientific Co., Ltd.) for 15 hours. Furthermore, it is left at room temperature (25 ° C.) for 24 hours. On the other hand, polyvinyl alcohol PVA235, degree of polymerization: 3,500, saponification value: 86 to 90% (manufactured by Kuraray);
Was added and stirred at 90 ° C. for 5 hours to dissolve the polyvinyl alcohol. And these two solutions and 10
0g of water and colloidal silica Snowtex XS
20 g (particle diameter: 2 to 6, granular, manufactured by Nissan Chemical Industries) was mixed and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating liquid. This coating solution is applied once on one side of a mirror at 90 ° C.
After heating and drying for 13 minutes at, the coating film surface was washed by flowing water for 5 minutes, and further heated and dried at 150 ° C. for 10 minutes to obtain a transparent coating film (film thickness: 10 μm).

[0157]

Example 24 10 g of zirconium nitrate dihydrate (manufactured by Wako Pure Chemical Industries) and 40 g of water were added and stirred for 5 minutes. Then, ion exchange resin WA-20 (manufactured by Mitsubishi Kasei); 30 g
And stir until the solution is at pH 3.0.
Thereafter, the solution and the ion exchange resin were separated by decantation, and the separated solution was placed in an oven (DK-
400, manufactured by Yamato Scientific Co., Ltd.) for 15 hours. Furthermore, it is left at room temperature (25 ° C.) for 24 hours. On the other hand, polyvinyl alcohol PVA235, degree of polymerization: 3,500, saponification value: 86 to 90% (manufactured by Kuraray);
Was added and stirred at 90 ° C. for 5 hours to dissolve the polyvinyl alcohol. And these two solutions and 10
0 g of water and colloidal silica Snowtex OL
(Particle size: 40 to 50, granular, manufactured by Nissan Chemical Industries) 20 g
Were mixed and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating liquid. This coating solution is applied once on one side of the mirror once,
After heating and drying at 0 ° C. for 13 minutes, the coating surface was washed by flowing water for 5 minutes, and further heated and dried at 150 ° C. for 10 minutes to obtain a transparent coating film (film thickness: 10 μm). .

[0158]

Comparative Example 1 In accordance with the components (parts by weight) shown in Table 1,
Water-absorbing coating composition 1 was prepared. First, a 25 wt% aqueous solution of polyacrylic acid and methanol were mixed, and stirred and dissolved at room temperature for 10 minutes to prepare a polymer solution 1.
Next, a binder solution 1 was prepared. First, a 2N aqueous hydrochloric acid solution, aluminum isopropoxide, and ethanol were mixed and stirred at room temperature for one day. Then, tetraethoxysilane tetramer (trade name: ethyl silicate 40, manufactured by Colcoat), silane coupling agent (trade name: SH60)
40, manufactured by Toray Dow Corning Co., Ltd., chemical name: γ-glycidoxypropyltrimethoxysilane) and stirred at room temperature for 10 minutes. Thereafter, after sufficiently hydrolyzing the tetraethoxysilane, N, N-dimethylbenzylamine was added, and the mixture was stirred at room temperature for 10 minutes to prepare a binder solution 1. Polymer solution 1 and binder composition 1
And stirred at room temperature for 10 minutes to prepare a water-absorbing coating liquid 1. The resulting liquid was a clear and viscous solution.

[0159]

[Table 1]

[0160]

Comparative Example 2 In accordance with the components (parts by weight) shown in Table 2,
Polyvinyl alcohol (degree of polymerization 1500-1800)
(Manufactured by Wako Pure Chemical Industries) was charged into water, and stirred at room temperature for one day to prepare a polymer solution. In addition, ethyl silicate 40 (manufactured by Colcoat); 6 g of a 2% aqueous nitric acid solution; 1 g and 54 g of methanol were added, and the mixture was stirred for 12 hours to carry out hydrolysis.
(Ethyl silicate hydrolyzed solution) A binder solution was prepared using the components shown in Table 2. Then, the polymer solution and the binder solution were mixed and stirred at room temperature for 10 minutes. The resulting liquid was a clear and viscous solution. This coating solution was applied once on one side of a mirror and heated and dried at 150 ° C. for 20 minutes to obtain a transparent coating film (film thickness: 2 μm).

[0161]

[Table 2]

[0162]

Comparative Example 3 A coating film (thickness: 2 μm) was obtained in the same manner as in Example 3 except that zirconium sulfate was changed to zirconium butoxide (manufactured by Wako Pure Chemical Industries, Ltd.).

[0163]

[Table 3]

[0164]

Comparative Example 4 0.4 g of zirconium oxychloride octahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and 19.6 g of water were added and stirred for 5 minutes. On the other hand, polyvinyl alcohol PVA217, degree of polymerization: 1,700, saponification value: 86 to 90% (manufactured by Kuraray); water; 93 g to 7 g, and stirred at 90 ° C. for 5 hours to dissolve the polyvinyl alcohol Was. Then, the two solutions were mixed and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating liquid. Apply this coating solution to one side of the mirror
The coating was repeated and heated and dried at 150 ° C. for 20 minutes to obtain a transparent coating film (film thickness: 2 μm).

[0165]

[Table 4]

[0166]

Comparative Example 5 10 g of zirconium nitrate dihydrate (manufactured by Wako Pure Chemical Industries) and 40 g of water were added and stirred for 5 minutes. On the other hand, polyvinyl alcohol PVA235, degree of polymerization: 3,
500, saponification value: 86 to 90% (manufactured by Kuraray); 5 g of water; 45 g were added, and the mixture was stirred at 90 ° C for 5 hours to dissolve polyvinyl alcohol. Then, the two solutions and 100 g of water were mixed and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating liquid. Apply this coating solution to one side of the mirror
After applying repeatedly, heating and drying at 90 ° C for 13 minutes,
The coating film surface was washed by flowing water for 5 minutes, and further heated and dried at 150 ° C. for 10 minutes to obtain a transparent coating film (film thickness;
10 μm).

[0167]

Comparative Example 6 10 g of zirconium nitrate dihydrate (manufactured by Wako Pure Chemical Industries) and 40 g of water were added and stirred for 5 minutes. Then, ion exchange resin WA-20 (manufactured by Mitsubishi Kasei); 30 g
And stir until the solution is at pH 3.0.
Thereafter, the solution and the ion exchange resin were separated by decantation, and the separated solution was placed in an oven (DK-
400, manufactured by Yamato Scientific Co., Ltd.) for 15 hours. Furthermore, it is left at room temperature (25 ° C.) for 24 hours. On the other hand, polyvinyl alcohol PVA235, degree of polymerization: 3,500, saponification value: 86 to 90% (manufactured by Kuraray);
Was added and stirred at 90 ° C. for 5 hours to dissolve the polyvinyl alcohol. And these two solutions and 10
0 g of water was mixed and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating liquid. This coating solution was applied once on one side of a mirror, and was heated and dried at 150 ° C. for 10 minutes. As a result, a transparent coating film (thickness: 10 μm) was obtained.

[0168]

Comparative Example 7 10 g of zirconium nitrate dihydrate (manufactured by Wako Pure Chemical Industries) and 40 g of water were added and stirred for 5 minutes. Then, ion exchange resin WA-20 (manufactured by Mitsubishi Kasei); 30 g
And stir until the solution is at pH 3.0.
Thereafter, the solution and the ion exchange resin were separated by decantation, and the separated solution was placed in an oven (DK-
400, manufactured by Yamato Scientific Co., Ltd.) for 15 hours. Furthermore, it is left at room temperature (25 ° C.) for 24 hours. On the other hand, polyvinyl alcohol PVA235, degree of polymerization: 3,500, saponification value: 86 to 90% (manufactured by Kuraray);
Was added and stirred at 90 ° C. for 5 hours to dissolve the polyvinyl alcohol. And these two solutions and 10
0 g of water and alumina sol-100 (particle size: 10-1
(G, 00, granular, manufactured by Nissan Chemical Industries, Ltd.) and stirred at room temperature (25 ° C.) for 30 minutes to obtain a coating solution. This coating solution was applied once on one side of a mirror, applied and heated and dried at 90 ° C. for 13 minutes.
Furthermore, when heated and dried at 150 ° C. for 10 minutes, a transparent coating film (film thickness: 10 μm) was obtained.

[0169]

[Table 5]

As shown in Tables 3, 4, and 5, the coatings processed as in the examples are effective in improving the alkali resistance, acid resistance, antifogging performance, appearance, and water resistance of the coatings.

[0171]

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. A composite material having good performance, drip properties, appearance, cleanability, and the like can be produced.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C09D 7/12 C09D 7/12 Z 129/04 129/04 B 185/00 185/00 G02B 1/04 G02B 1/04 G02C 7/02 G02C 7/02 F term (reference) 3B111 AA01 AC01 AD01 CA03 4D075 CA04 CA34 CA37 CA39 CA44 DA04 DB13 DC24 EA06 EC10 EC35 EC47 4J038 BA021 BA091 BA141 CE021 CG011 CG171 HA121 DM01012 DF01022 HA146 HA226 HA256 HA336 HA346 HA376 HA446 HA466 JA11 JA19 JA35 JA37 JA65 JA66 JB03 JB10 JB22 JB23 JB32 JB35 JB38 JC22 JC26 JC29 JC33 JC37 JC38 JC41 KA04 KA09 KA20 LA06 MA07 MA08 MA10 NA01 NA04 NA03 PA17 PA19

Claims (46)

[Claims] 1. A composition for absorbing the surface of a member to which it is applied, comprising: (a) at least one selected from zirconyl, zirconium nitrate, zirconium sulfate, and zirconium halide; and (b) water absorption. A composition comprising at least a hydrophilic organic polymer and (c) a solvent. 2. The composition according to claim 1, wherein the solvent is water or a water-containing organic solvent. 3. The composition according to claim 1, wherein the zirconyl is zirconium oxychloride. 4. The composition according to claim 1, wherein the zirconium halide is zirconium chloride. 5. The composition according to claim 1, wherein the water-absorbing organic polymer contains at least polyvinyl alcohol. 6. The method of claim 1, further comprising a catalyst.
A composition according to any one of the preceding claims. 7. The composition according to claim 6, wherein the catalyst is a hydrolysis catalyst and / or a curing catalyst. 8. The composition according to claim 1, further comprising an inorganic alkoxide and / or a polymer having an OH group formed by hydrolysis and polycondensation of the inorganic alkoxide. . 9. The composition according to claim 1, further comprising a fluorinated surfactant containing a hydrophilic group. 10. The composition according to claim 1, further comprising a heat ray absorbing material. 11. The method according to claim 1, further comprising a heat storage material.
The composition according to any one of claims 10 to 10. 12. The composition according to claim 1, further comprising an ultraviolet absorbent. 13. The composition according to claim 1, further comprising an antimicrobial metal or a compound thereof. 14. The composition according to any one of claims 1 to 13, further comprising photocatalyst particles, which exhibits hydrophilicity when the surface of a member to which the photocatalyst particles are applied is irradiated with light. 15. The composition according to claim 14, wherein said photocatalytic particles are anatase type titanium oxide. 16. The composition according to claim 1, further comprising at least one metal selected from the group consisting of Pt, Pd, Rh, Ru, Os and Ir. 17. The composition according to claim 1, which imparts anti-fogging property to the surface of the member to which it is applied. 18. At the surface of the member to which it is applied, moisture condensate and / or water droplets adhering to the surface are allowed to absorb on the surface of the coating, whereby the surface condenses the moisture. 17. 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. 19. The composition according to claim 1, wherein on the surface of the member to which it is applied, contaminants adhering to the surface are easily washed off by water. . 20. The composition according to claim 1, which imparts anti-dew properties to the surface of the member to which the composition is applied. 21. The composition according to claim 1, which imparts humidity control to the surface of the member to which the composition is applied. 22. The composition according to claim 1, which imparts drip properties to the surface of the member to which it is applied. 23. A part or all of at least one selected from the above (a) is dissolved in the solvent of the above (c), and the solution is kept in an atmosphere of 50 ° C. or more for 1 hour or more. The composition according to any one of claims 1 to 22, wherein the solution is mixed with (b). 24. After dissolving a part or all of at least one kind selected from the above (a) with the solvent of the above (c), and keeping the solution in an atmosphere of 90 ° C. or more for 1 hour or more. The composition according to any one of claims 1 to 22, wherein the solution is mixed with (b). 25. The composition according to claim 1, wherein the composition is kept in an atmosphere at 50 ° C. or more for 1 hour or more. 26. The composition according to claim 1, wherein the composition is kept in an atmosphere at 90 ° C. or more for 1 hour or more. 27. The composition has an average particle size of 0.1 n.
The composition according to any one of claims 23 to 26, having zirconia of m to 100 nm. 28. The composition further comprises an average particle size of 5
The composition according to any one of claims 23 to 27, wherein an inorganic oxide having a thickness of from 200 nm to 200 nm is mixed. 29. The composition according to claim 28, wherein said inorganic oxide is silica. 30. The method for preparing a composition according to any one of claims 1 to 22, 27, and 28, wherein a part or all of at least one selected from the above (a) is used. Dissolved in the solvent of the above (c), and the solution was kept in an atmosphere of 50 ° C. or more for 1 hour or more, and then the solution was added to the above (b).
And a method for preparing a composition. 31. The method for preparing a composition according to any one of claims 1 to 22, 27, and 28, wherein a part or all of at least one selected from the above (a) is used. Dissolved in the solvent of the above (c), and after keeping the solution in an atmosphere of 90 ° C. or more for 1 hour or more, the solution was mixed with the above (b)
And a method for preparing a composition. 32. A method for preparing a composition, wherein the composition according to any one of claims 1 to 24 is kept in an atmosphere at 50 ° C. or higher for 1 hour or longer. 33. A method for preparing a composition, wherein the composition according to claim 1 is kept in an atmosphere at 90 ° C. or higher for 1 hour or longer. 34. A method for producing a member having a hygroscopic surface, comprising applying the composition according to any one of claims 1 to 29 to the surface of the member and drying or curing the composition. A production method comprising: 35. The method according to claim 34, comprising cleaning the surface of the member with a cleaning agent before applying the composition to the surface of the member. 36. The washing, wherein the washing is a ceria-containing solution.
The method according to claim 34. 37. The method according to claim 34, further comprising pre-hydrophilizing the surface of the member before applying the composition to the surface of the member. 38. The production method according to claim 37, wherein the hydrophilization is irradiation with ultraviolet light having a wavelength of 260 nm or less. 39. The hydrophilization is a corona discharge treatment,
A method according to claim 37. 40. The method according to claim 34, wherein the member is transparent and the resulting hygroscopic surface is also transparent. 41. A method for producing a member having a hygroscopic surface, comprising applying the composition according to any one of claims 1 to 29 to the surface of the member, and applying the composition at a first temperature of 50 to 150 ° C. After drying or hardening and cleaning the member surface with water and / or an organic solvent, the temperature is higher than the first temperature and 60
A manufacturing method comprising drying or curing at a second temperature of -200 <0> C. 42. A member obtained by the method according to any one of claims 34 to 41, the surface of which is made hygroscopic. 43. The member according to claim 42, wherein said member is a mirror. 44. The member according to claim 42, wherein the member is a transparent plate-shaped member. 45. The member according to claim 42, wherein said member is a transparent lens. 46. The member according to claim 42, wherein said member is a transparent film.