JP2003049117A - Hydrophilic coating composition and its coated article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrophilic coating composition which gives coating films maintaining the same or higher water resistance and abrasion resistance as or than those of conventional hydrophilic coating compositions and capable of exhibiting antifogging property from an early time after formed without being irradiated with UV light, and to provide its coated article. SOLUTION: This hydrophilic coating composition comprises a silicone resin and an organic Zr compound. A hydrophilic coated article comprises a substrate and a coating layer comprising a cured coating film of the hydrophilic coating composition and formed on the surface of the substrate.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a hydrophilic coating material composition having antifogging property and a coated article thereof.

[0002]

2. Description of the Related Art A coating film obtained from a coating material containing a silicone resin consisting of a hydrolyzate and / or a partial hydrolyzate of a tetrafunctional alkoxide and an inorganic filler has a low contact angle with water and shows antifogging property. It is also known to have high wear resistance. In addition, Japanese Patent Laid-Open No. 2001-146
According to Japanese Patent No. 573, 250 to 3 after applying the coating material
A higher antifogging property can be obtained by curing at a firing temperature of 50 ° C.

Further, in a coating film obtained by applying and curing a coating material containing silicone resin as a main component and containing an optical semiconductor, various effects as described below can be expected,
It is applied to various base materials.

Excitation wavelengths (eg 400 n
When exposed to the light (ultraviolet light) of m), active oxygen capable of oxidatively decomposing organic substances is generated. Therefore, the material coated with a paint containing an optical semiconductor on the surface of the base material is carbon. Self-cleaning effect that decomposes system dirt components (for example, carbon fractions contained in automobile exhaust gas, cigarette tar, etc.); Deodorizing effect that decomposes malodorous components represented by amine compounds and aldehyde compounds;
Antibacterial effect that prevents the generation of bacterial components represented by Escherichia coli and Staphylococcus aureus; antifungal effect is expected. Further, when the material coated with a coating material containing a photo-semiconductor is exposed to ultraviolet rays, the photo-semiconductor photocatalysts the photo-semiconductor to hydrolyze the moisture in the air or the moisture adhering to the surface of the material to form a hydroxyl radical. Hydroxyl radicals decompose and remove water-repellent organic substances and the like (those attached to the surface of the material and those contained in the surface of the material), whereby the contact angle of water with respect to the surface of the material is reduced and the surface of the material is reduced. Also has the effect of improving hydrophilicity (water wettability), that is, it becomes easier to get wet (familiar) with water. Due to this hydrophilicity improving effect, in indoor members,
It is expected that the glass and the mirror will be less likely to be fogged by water drops, and that the outdoor member will have an antifouling effect that the attached dirt is washed off by rainwater. Further, the material in which the base material surface is coated with a coating material containing an optical semiconductor also has an antistatic function due to the photocatalytic action of the optical semiconductor, and this function is also expected to have an antifouling effect.

[0005]

However, the above-mentioned prior art has the following problems. This is because when the silicone resin is mainly composed of a tetrafunctional silicone resin, the hydrophilicity may be insufficient in the initial stage after film formation, and when a photo-semiconductor is contained, the photo-catalyst after being irradiated with ultraviolet rays may be used. Since it takes some time for the action to be exerted, the hydrophilicity is not obtained until the photocatalytic action is exerted after film formation, and it does not easily become hydrophilic in an indoor place where ultraviolet rays are not exposed. , It was hard to use. Further, in the technique of Japanese Patent Laid-Open No. 2001-146573, it is necessary to bake at a temperature of 250 to 350 [deg.] C. Therefore, when applying it to a base material having low heat resistance, or applying it to the outer wall of a building, it cannot be heated. There is a problem that it cannot be applied when applied to various places.

Therefore, an object of the present invention is to provide a hydrophilic coating capable of exhibiting antifogging properties from the initial stage after film formation without irradiation of ultraviolet rays while maintaining water resistance and abrasion resistance equal to or higher than those of the above-mentioned prior art. To provide a wood composition and a coated product thereof.

[0007]

In order to solve the above problems, the present inventor has made various studies. As a result, by experimenting with the silicone resin containing the following specific organometallic compounds, it was possible to exhibit antifog properties without irradiating ultraviolet rays from the initial stage of film formation without lowering water resistance, abrasion resistance, etc. Then, the hydrophilic coating composition and the hydrophilic coated article of the present invention were completed.

In the present invention, "hydrophilic" means that the hydrophilicity is excellent from the beginning.

The hydrophilic coating material composition according to claim 1 of the present invention contains a silicone resin and an organic Zr compound.

The hydrophilic coating according to claim 2 of the present invention
The coating composition is a hydrophilic coating according to claim 1 of the present invention.
In the coating composition, the organic Zr compound is Z
rO _nR¹ _m(OR²)_pIs a compound represented by. (here
And R¹And R²Are the same or different monovalent organic groups or
Represents a hydrogen atom, p is an integer of 1 to 4, and n is 0 or 1.
And 2n + m + p = 4. ) Hydrophilic coating material composition according to claim 3 of the present invention
Is the hydrophilic coating material according to claim 1 of the present invention.
In the composition, the organic Zr compound is Zr (C _FiveH₇O
₂)_FourIs.

The hydrophilic coating material composition according to claim 4 of the present invention is the hydrophilic coating material composition according to claim 1 of the present invention, wherein the organic Zr compound is Z.
r (OC ₄ H ₉ ) (C ₅ H ₇ O ₂ ) (C ₆ H ₉ O ₃ ) ₂ .

The hydrophilic coating material composition according to claim 5 of the present invention is the hydrophilic coating material composition according to any one of claims 1 to 4 of the present invention, wherein the organic Z
The r compound is contained in an amount of 0.1 to 30% by weight based on the total solid content of the hydrophilic coating material composition.

The hydrophilic coating material composition according to claim 6 of the present invention is the hydrophilic coating material composition according to any one of claims 1 to 5 of the present invention, which further contains an inorganic filler.

The hydrophilic coating material composition according to claim 7 of the present invention is the hydrophilic coating material composition according to claim 6 of the present invention, wherein the inorganic filler is an optical semiconductor.

The hydrophilic coating material composition according to claim 8 of the present invention is the hydrophilic coating material composition according to claim 7 of the present invention, wherein the optical semiconductor is anatase type TiO ₂ .

The hydrophilic coated article according to claim 9 of the present invention is
The surface of the base material is provided with a coating layer comprising a coating and cured film of the hydrophilic coating material composition according to any one of claims 1 to 8 of the present invention.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Silicone resin, which is one of the essential components of the hydrophilic coating material composition of the present invention, is a component used as a binder resin and a film forming component.

The form of the silicone resin is not particularly limited, and may be, for example, a solution form or a dispersion form.

The silicone resin is generally a (partial) hydrolyzate of a hydrolyzable organosilane represented by the following formulas (1) to (3). In the present specification, “(partial) hydrolysis” means “partial hydrolysis and / or hydrolysis”.

Si (OR) ₄ (1) R ¹ Si (OR) ₃ (2) (R ¹ ) ₂ Si (OR) ₂ (3) R in the formulas (1) to (3) is a monovalent carbon. It is not particularly limited as long as it is a hydrogen group, but a monovalent hydrocarbon group having 1 to 8 carbon atoms is preferable, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a peptyl group,
An alkyl group such as an octyl group can be exemplified. Among these alkyl groups, those having 3 or more carbon atoms may be linear groups such as n-propyl group and n-butyl group, or may be isopropyl group, isobutyl group, t-butyl group. It may have a branch such as a group. R ¹ in formulas (2) and (3) is not particularly limited as long as it is a monovalent hydrocarbon group, but is not limited to methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, peptyl group. In addition to alkyl groups such as groups and octyl groups, γ-glycidoxypropyl groups and the like are also exemplified.

Examples of the hydrolyzable organosilane represented by the formula (1) include tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane and tetra-t-butoxysilane.

Examples of the hydrolyzable organosilane represented by the formula (2) include γ-glycidoxypropyltrimethoxysilane.

Examples of the hydrolyzable organosilane represented by the formula (3) include γ-glycidoxypropylmethyldimethoxysilane.

The hydrolyzable organosilane may be used alone or in combination of two or more.

The silicone resin is prepared, for example, by adding water as a curing agent and, if necessary, a catalyst and the like in a necessary amount to a hydrolyzable organosilane to cause (partial) hydrolysis to form a prepolymer. It can be prepared.

The silicone resin is prepared, for example, by adding water as a curing agent and a necessary amount of a catalyst and the like to a hydrolyzable organosilane and performing (partial) hydrolysis to form a prepolymer. It can be prepared.

The amount of water used for (partial) hydrolysis of the hydrolyzable organosilane is not particularly limited, but for example, water (H) relative to the hydrolyzable group (OR) of the hydrolyzable organosilane is used. ₂ O), the molar equivalent ratio (H ₂ O / OR) is preferably 0.3 to 5, more preferably 0.35 to 4, and still more preferably 0.4 to
It is in the range of 3.5. If the molar equivalent ratio is less than 0.3, hydrolysis does not proceed sufficiently and the cured coating may become brittle, and if it exceeds 5, the resulting silicone range tends to gel in a short time. , The storage stability may be reduced.

In addition, the hydrolyzable organosilane (partial)
The catalyst used as necessary during the hydrolysis is not particularly limited, but an acidic catalyst is preferable from the viewpoint of shortening the time required for the production process. The acidic catalyst is not particularly limited, and examples thereof include acetic acid, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, toluenesulfonic acid, and oxalic acid. Examples thereof include organic acids such as acids; inorganic acids such as hydrochloric acid, nitric acid and silane halides; acidic colloidal silica, acidic sol fillers such as titania oxide sol, and the like, and one or more of them can be used.

The (partial) hydrolysis of the hydrolyzable organosilane may be carried out by heating (eg, 40 to 100 ° C.) as necessary.
It may be heated).

The (partial) hydrolysis of the hydrolyzable organosilane may be carried out by diluting the hydrolyzable organosilane with a suitable solvent, if necessary. The diluent solvent (reaction solvent) is not particularly limited, but, for example,
Lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol;
Ethylene glycol derivatives such as ethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether acetate; diethylene glycol,
Examples include diethylene glycol derivatives such as diethylene glycol monobutyl ether; and diacetone alcohol, and one or more selected from the group consisting of these can be used. In combination with these hydrophilic organic solvents, toluene, xylene,
One or more of hexane, heptane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime and the like can be used.

The weight average molecular weight (Mw) of the silicone resin used in the present invention is not particularly limited, but is preferably in the range of 500 to 1000 in terms of polystyrene. If it is less than 500, the silicone resin is unstable, and if it is more than 1000, the coating film cannot maintain sufficient hardness.

The hydrophilic coating material composition of the present invention comprises
In addition to the silicone resin, it further contains an organic Zr compound as an essential component. The organic Zr compound accelerates the condensation reaction by dehydration / dealcoholization, increases the cross-linking density of the coating film, improves the adhesion to the base material, the effect of hardening the film, and further the hydrophobicity, water resistance and resistance. Has an alkaline effect and the like.

Examples of the organic Zr compound include ZrO _n R ¹ _m (OR ² ) _p (wherein R ¹ and R ² represent the same or different monovalent organic groups or hydrogen atoms, and p is 1 to 4). An integer, n is 0 or 1, and 2n + m + p = 4) is preferably used. Especially Zr (OC ₄ H ₉ ) ₃
(C ₅ H ₇ O ₂ ) and Zr (OC ₄ H ₉ ) (C ₅ H ₇ O ₂ )
When (C ₆ H ₉ O ₃ ) ₂ is used, even if it is dried at room temperature after the coating of the coating material, it shows a higher antifogging property than the initial stage, as in the case of baking at about 300 ° C.

The content of the organic Zr compound is preferably 0.1 to 30% by weight based on the total solid content of the hydrophilic coating material composition. If it is less than 0.1% by weight, the effect of addition may not be seen, and if it exceeds 30% by weight, gelation or aggregation of the coating material may occur.

The hydrophilic coating material composition of the present invention comprises
You may also contain the filler as needed. The filler is not particularly limited, and known fillers such as inorganic fillers such as silica, alumina, inorganic oxides such as optical semiconductors; organic fillers such as carbon black can be used. Among these, inorganic fillers are particularly preferable from the viewpoint of chemical stability such as solvent resistance and acid resistance, dispersibility in a silicone resin, and abrasion resistance of a cured film.
Only one type of filler may be used, or two or more types may be used in combination.

The form of silica used as the inorganic filler is not particularly limited, and may be, for example, a powder form or a sol form (colloidal silica). The colloidal silica is not particularly limited, but, for example, water-dispersible or non-aqueous organic solvent-dispersed colloidal such as alcohol can be used. Generally, such colloidal silica has a silica content of 20 to 20 as a solid content.
The content of silica is 50% by weight, and the content of silica can be determined from this value. When water-dispersible colloidal silica is used, water present as a component other than solid content in the colloidal silica can be used for (partial) hydrolysis of hydrolyzable organosilane ((partial) hydrolysis). Will be added to the amount of water used). Water-dispersible colloidal silica is usually made from water glass, but it is easily available as a commercial product. The organic solvent-dispersible colloidal silica can be easily prepared by replacing the water of the water-dispersible colloidal silica with an organic solvent.
Such an organic solvent-dispersible colloidal silica can be easily obtained as a commercial product like the water-dispersible colloidal silica. In the organic solvent-dispersible colloidal silica, the type of organic solvent in which the colloidal silica is dispersed is not particularly limited, but examples thereof include lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol; ethylene. Examples include ethylene glycol derivatives such as glycol, ethylene glycol monobutyl ether, and acetic acid ethylene glycol monoethyl ether; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and diacetone alcohol. One selected from the group consisting of these. Alternatively, two or more kinds can be used. In combination with these hydrophilic organic solvents, one or more of toluene, xylene, hexane, heptane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime and the like can be used.

The hydrophilic coating material composition of the present invention comprises
In addition to obtaining various functions due to the photocatalytic effect described later,
In order to further increase the surface hydrophilicity of the formed coating film by the photocatalytic effect or to maintain it for a long period of time, it is preferable to include an optical semiconductor as the inorganic filler.

The optical semiconductor is not particularly limited, but examples thereof include titanium oxide, zinc oxide, tin oxide, iron oxide, zirconium oxide, tungsten oxide, chromium oxide, molybdenum oxide, ruthenium oxide, germanium oxide, lead oxide, and oxide. Examples include metal oxides such as cadmium, copper oxide, vanadium oxide, niobium oxide, tantalum oxide, manganese oxide, cobalt oxide, rhodium oxide, nickel oxide, and rhenium oxide, and strontium titanate. Among these, the above metal oxides are preferable in that they can be practically easily used, and titanium oxide is particularly preferable among the metal oxides because of its photocatalytic performance, curing acceleration performance, safety, easy availability and cost. It is preferable from the aspect. In addition,
When titanium oxide is used as an optical semiconductor, it is better to use one whose crystal type is anatase type (anatase type).
It is preferable in that the photocatalytic performance and the curing promotion performance are the strongest, and the photocatalytic performance and the curing promotion performance are exhibited in a shorter time as well as the long-term development.

Only one kind of optical semiconductor may be used, or 2
You may use it in combination of 2 or more types.

As the raw material of the optical semiconductor, any material that finally exhibits the properties of the optical semiconductor can be used.

Excitation wavelength (for example, 400 n
It is known that active oxygen is generated when exposed to the light (ultraviolet light) of m). Since active oxygen can oxidize and decompose organic substances, a material having a coating material composition containing an optical semiconductor coated on the surface of a substrate has a carbon-based fouling component (for example, an automobile) attached to the surface. Self-cleaning effect that decomposes carbon fractions contained in exhaust gas, cigarette tar, etc .; Deodorizing effect that decomposes malodorous components represented by amine compounds and aldehyde compounds; represented by Escherichia coli and Staphylococcus aureus Antibacterial effect that prevents the generation of bacterial components; antifungal effect, etc. are expected. In addition, when the material coated with the coating material composition containing the photo-semiconductor is exposed to ultraviolet rays, the photo-semiconductor has a photocatalytic action to remove the water in the air or the water adhering to the surface of the material by hydroxyl radicals. And the hydroxide radical decomposes and removes water-repellent organic substances and the like (those attached to the surface of the material and those contained in the surface of the material), whereby the contact angle of water with respect to the surface of the material decreases. Hydrophilicity (water wettability) that the surface of the material is easily wetted by water
There is also an improvement effect. Due to this hydrophilicity improving effect, it is expected that an indoor member has an antifogging effect in which glass and a mirror are less likely to be fogged by water droplets, and an outdoor member has an antifouling effect in which adhered dirt is washed by rainwater. Furthermore, there is also an antistatic function due to the photocatalytic action of the optical semiconductor, and this function further improves the antifouling effect.

The above-mentioned filler may be in any form as long as it can be dispersed in the coating material composition, such as powder, fine particle powder, solution-dispersed sol particles, etc., but in the form of a sol, particularly a sol having a pH of 7 or less. If so, curing proceeds in a shorter time and is convenient in use.

The dispersion medium to be used is not particularly limited as long as it can uniformly disperse the filler, and either an aqueous solvent or a non-aqueous solvent can be used.

The aqueous solvent is not particularly limited, but, for example, in addition to water alone, a hydrophilic organic solvent (for example, methanol, ethanol, isopropanol, n-).
Lower aliphatic alcohols such as butanol and isobutanol; ethylene glycol derivatives such as ethylene glycol, ethylene glycol monobutyl ether and acetic acid ethylene glycol monoethyl ether; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; diacetone alcohol) A mixed solvent of seed and water can be used. Among these aqueous solvents, a water-methanol mixed solvent is preferable from the viewpoint of dispersion stability of the filler and drying property of the dispersion medium after coating. Furthermore, by using an aqueous sol, it is possible to have it also function as an acidic catalyst during (partial) hydrolysis of the hydrolyzable organosilane.

The non-aqueous solvent that can be used as the dispersion medium for the filler is not particularly limited, but is selected from the group consisting of the above-mentioned hydrophilic organic solvent and a hydrophobic organic solvent such as toluene or xylene. At least one organic solvent can be used. Among these non-aqueous solvents, methanol is preferable in terms of dispersion stability of the filler and drying property of the dispersion medium after coating.

The method for uniformly dispersing the filler in the dispersion medium is not particularly limited, and for example,
Various ordinary dispersing methods using a homogenizer, a disper, a paint shaker, a bead mill, etc. can be used.

The method for producing the hydrophilic coating material composition of the present invention is not particularly limited, and the respective components may be mixed using a conventional method and apparatus.

The hydrophilic coated article of the present invention has the following properties:
It is provided with a coating layer composed of a coated and cured film of the hydrophilic coating composition of the present invention.

The method for applying the hydrophilic coating material composition of the present invention is not particularly limited, and for example, brush coating, spray coating, dipping (dipping,
Ordinary various coatings such as dip coating, roll coating, flow coating (flow coating method in which paint is poured from the top of the base material to be coated), curtain coating, knife coating, spin coating, bar coating, etc. You can choose the method.

As a method for curing the coating film of the hydrophilic coating material composition of the present invention, a known method may be used,
There is no particular limitation. Further, the temperature at the time of curing is not particularly limited, and may be in a wide range from normal temperature to heating temperature depending on desired cured film performance, heat resistance of the filler and the base material, and the like.

As the base material to which the hydrophilic coating material composition of the present invention is applied (which is also the base material used in the hydrophilic coated article of the present invention), various kinds of base materials may be used regardless of organic or inorganic. But is not particularly limited, for example,
Examples thereof include glass, metal and plastic. These substrates are preferably pre-washed so that a coating film can be formed uniformly during coating, or in order to improve adhesion with the coating film. The method is not particularly limited, but examples thereof include alkali cleaning, ammonium fluoride cleaning, plasma cleaning, and UV cleaning.

[0052]

The present invention will be described in detail below with reference to Examples and Comparative Examples. In Examples and Comparative Examples, all "parts" represent "parts by weight" and all "%" represent "% by weight" unless otherwise specified. The molecular weight is measured by GPC (gel permeation chromatography) using HLC8020 manufactured by Tosoh Corporation as a measurement model to prepare a calibration curve using standard polystyrene, and measuring the calibration curve. The present invention is not limited to the examples below.

Example 1 Tetraethoxysilane 208
356 parts of methanol was added to the parts, 18 parts of water and 18 parts of 0.01N hydrochloric acid were further mixed, and well mixed using a disper to obtain a coating solution. The obtained liquid was heated in a constant temperature bath at 60 ° C. for 2 hours to adjust the weight average molecular weight to 950, whereby a silicone resin (A) was obtained.

Next, to this silicone resin (A), a titanium oxide water sol (solid content 21%, average primary particle diameter 20 nm) was added as a filler component (photosemiconductor) to a photosemiconductor / all-silicone resin (condensation compound equivalent). It was added so that the weight ratio was 1.0 based on the solid content, and diluted with methanol so that the total solid content was 5% to obtain a basic coating material.
As an organic Zr compound, Zr (OC ₄ H ₉ ) ₃ (C ₅ H
₇ O ₂ ) was added to the solid content of the basic coating material in an amount of 1% to obtain a hydrophilic coating material composition.

After this was left for 1 hour, the glass substrate was coated with a spin coater and baked at 300 ° C. to prepare a hydrophilic coated article.

<Example 2> In Example 1, the organic Zr
As a compound, Zr (OC ₄ H ₉ ) (C ₅ H ₇ O ₂ ) (C ₆ H ₉
A hydrophilic coating material composition was obtained in the same manner as in Example 1 except that O ₃ ) ₂ was added. Then, using this hydrophilic coating material composition, a hydrophilic coated article was produced in the same manner as in Example 1.

<Example 3> In Example 1, the organic Zr
The compound addition amount is 20 with respect to the basic coating material solid content.
A hydrophilic coating material composition was obtained by performing the same operation as in Example 1 except that the content was changed to%. Then, using this hydrophilic coating material composition, a hydrophilic coated article was produced in the same manner as in Example 1.

<Example 4> In Example 2, the organic Zr
The compound addition amount is 20 with respect to the basic coating material solid content.
A hydrophilic coating material composition was obtained by performing the same operation as in Example 2 except that the content was changed to%. Next, using this hydrophilic coating material composition, a hydrophilic coated article was produced in the same manner as in Example 2.

Example 5 A hydrophilic coating material composition was obtained in the same manner as in Example 3, except that the drying temperature was 30 ° C. Next, using this hydrophilic coating material composition, a hydrophilic coated article was produced in the same manner as in Example 3.

Example 6 In Example 1, silica methanol sol (trade name: methanol silica sol, manufactured by Nissan Kagaku Kogyo Co., Ltd., particle size 10 to 20 nm) was used as a filler component and a solid of filler / all silicone resin (condensation compound conversion). A hydrophilic coating material composition was obtained in the same manner as in Example 1 except that the weight ratio was 0.25 on a minute basis. Then, using this hydrophilic coating material composition, a hydrophilic coated article was produced in the same manner as in Example 1.

Comparative Example 1 A coated article is prepared in the same manner as in Example 1 except that the basic coating material is applied to the glass substrate without adding the organic Zr compound to the basic coating material. did.

Comparative Example 2 A coated article is prepared in the same manner as in Example 5 except that the basic coating material is applied to the glass substrate without adding the organic Zr compound to the basic coating material. did.

Comparative Example 3 A coated article is prepared in the same manner as in Example 6 except that the basic coating material is applied to the glass substrate without adding the organic Zr compound to the basic coating material. did.

[Evaluation of coating film performance] The coating film performance of the coated article obtained as described above was evaluated by the following method.

(Contact Angle with Water) After the coating film was formed, it was sufficiently cooled to room temperature under the condition that it was not exposed to ultraviolet rays, and the contact angle with water was measured.

The evaluation results are shown in Table 1.

[0067]

[Table 1] As shown in Table 1, in each of Examples 1 to 6, the contact angle was less than 10 °. On the other hand, in Comparative Examples 1 to 3 in which the organic Zr compound was not used, the contact angle was more than 30 °. From this, it can be seen that the use of the organic Zr compound exhibits excellent antifogging property immediately after the coating film is formed.

[0068]

EFFECT OF THE INVENTION The hydrophilic coating material composition of the present invention exhibits antifogging property without irradiation of ultraviolet rays from the initial stage after film formation.

The hydrophilic coated article of the present invention is provided with a coating layer consisting of the coating and cured film of the hydrophilic coating material composition of the present invention, and therefore exhibits antifogging property without irradiation of ultraviolet rays from the initial stage after film formation.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Keishi Shibata             1048, Kadoma, Kadoma-shi, Osaka Matsushita Electric Works             Within the corporation F-term (reference) 4J038 DL021 DL031 DL051 DM022                       HA216 HA446 KA06 KA08                       MA14 NA05 NA06

Claims (9)

[Claims] 1. A hydrophilic coating material composition containing a silicone resin and an organic Zr compound. 2. The organic Zr compound is ZrO _n R ¹ _m (O
The hydrophilic coating material composition according to claim 1, which is a compound represented by R ² ) _p . (Here, R ¹ and R ² represent the same or different monovalent organic groups or hydrogen atoms, p is an integer of 1 to 4, n is 0 or 1, and 2n + m + p =
It is 4. ) 3. The organic Zr compound is the ZrO _n R ¹ _m
The compound represented by (OR ² ) _p is Zr (OC ₄ H ₉ )
The hydrophilic coating material composition according to claim 1, which is ₃ (C ₅ H ₇ O ₂ ). 4. The organic Zr compound is Zr (OC ₄ H ₉ )
The hydrophilic coating material composition according to claim 1, which is (C ₅ H ₇ O ₂ ) (C ₆ H ₉ O ₃ ) ₂ . 5. The hydrophilic coating material composition according to claim 1, which contains the organic Zr compound in an amount of 0.1 to 30% by weight based on the total solid content of the hydrophilic coating material composition. 6. The method according to any one of claims 1 to 5, further comprising an inorganic filler.
5. The hydrophilic coating material composition according to any one of 1. 7. The hydrophilic coating material composition according to claim 6, wherein the inorganic filler is an optical semiconductor. 8. The hydrophilic coating material composition according to claim 7, wherein the optical semiconductor is anatase type TiO ₂ . 9. A hydrophilic coated article having a coating layer formed on the surface of a base material, the coating layer comprising the coated and cured coating of the hydrophilic coating material composition according to any one of claims 1 to 8.