JP3424533B2 - Hydrophilic inorganic paint and hydrophilic paint using it - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an antifogging property, an antifouling property,
The present invention relates to a hydrophilic inorganic paint capable of forming a film excellent in functions such as weather resistance and durability, and a hydrophilic coated product using the same.

[0002]

2. Description of the Related Art A paint containing an optical semiconductor is known as a paint capable of forming a coating film having excellent functions such as antifogging property and antifouling property (JP-A-61-83106). Publication, see WO96 / 29375). When a coating film containing a photo-semiconductor is exposed to ultraviolet rays, its photo-catalytic action causes the photo-semiconductor to decompose organic substances that repel water (those that adhere to the surface of the coating film and those that are contained in the coating film). A hydrophilic (water wettability) improving effect is obtained in which the contact angle of water with respect to the surface is reduced and the coating film surface is easily wetted (compatible) with water. From this hydrophilicity improving effect, indoor members are expected to have an antifogging effect in which glass and mirrors are less likely to be fogged by water drops, and outdoor members are expected to have an antifouling effect in which adhered dirt is washed by rainwater. .

[0003]

However, as described above,
A coating film formed from a coating material containing an optical semiconductor requires some time for the optical semiconductor to exert its effect after being exposed to ultraviolet light, so after the film is formed, until the effect of the optical semiconductor is exerted. However, there were problems that surface hydrophilicity could not be obtained, stains were likely to adhere, fogging was likely to occur, and the effect was difficult to understand. Further, there is a problem in that it is difficult to use because it takes a longer time for the optical semiconductor to exert its effect in a place not exposed to ultraviolet rays.

As a measure for solving these problems,
It is possible to add a surfactant to the paint. Since surfactants have the effect of improving hydrophilicity, it is expected that the addition of surfactants will provide surface hydrophilicity from the beginning of film formation and exhibit antifogging and antifouling properties. It However, a general surfactant has a problem that it deteriorates with the passage of time or flows off from the surface of the coating film. Therefore, it is difficult to exhibit the surface hydrophilicity of the coating film for a long period of time.

Therefore, an object of the present invention is to provide a hydrophilic inorganic paint capable of exhibiting surface hydrophilicity from the beginning of film formation and forming a coating film whose surface hydrophilicity continues for a long period of time.
A hydrophilic coated article using the same is provided.

[0006]

In order to solve the above problems, the present inventors have made various studies. As a result, they have found the following things and completed the present invention. That is,
When a silane-modified surfactant having a reactive group at the terminal is added to an inorganic coating material containing a silicone resin as a main component, the above-mentioned surfactant undergoes a crosslinking reaction with the silicone resin to form a matrix of the silicone resin (crosslinked structure). )
Since it is possible to obtain a coating film taken in and fixed in the inside, the surfactant is less likely to deteriorate with time and flow off from the surface of the coating film. That is, while being exhibited, the surface hydrophilicity will continue for a long period of time.

Namely, the hydrophilic inorganic coating of the present invention, especially
A specific silane-modified surfactant having a reactive group at the end (hereinafter, may be simply referred to as "silane-modified surfactant") is contained in an inorganic coating material containing a fixed silicone resin as a main component. It becomes. The silane-modified surfactant is a compound represented by the following following general formula (a).

General formula R ⁰ _n SiX _4-n (a) (In the formula, R ⁰ represents the same or different hydrophilic group, and n is 1
~ 3, X represents a hydrolyzable group. ) The silicone resin is the following silicone resin (1)
Alternatively, (2) is preferable.

The silicone resin (1) contains the following component (A). Component (A): (A ₁ ) With respect to 1 mol of the silicon compound represented by the general formula R ² Si (OR ¹ ) ₃ , (A ₂ ) General formula Si (OR ¹ ) ₄
0.1 to 20 mol of a silicon compound represented by and / or colloidal silica, and (A ₃ ) general formula R ² ₂ Si (O
A hydrolyzable polycondensate of a hydrolyzable mixture containing 0 to 0.6 mol of a silicon compound represented by R ¹ ) ₂ (wherein R ¹ and R ² represent a monovalent hydrocarbon group), , The weight average molecular weight of this hydrolyzed polycondensate is 90 in terms of polystyrene.
An organosiloxane adjusted to be 0 or more (hereinafter, this may be referred to as "organosiloxane (A)").

When the silicone resin (1) is used as the silicone resin, the silane-modified surfactant is an all-silicon compound (excluding colloidal silica) 1 which is a raw material of the component (A) when the component (A) is prepared. It is preferable to add it in the paint by adding it in an amount of 0.025 to 1 mol per mol.

The silicone resin (2) is the following (B),
Organosilanes containing components (C), (D) and (E), and at least 50 mol% of the hydrolyzable organosilane as the raw material of component (B) are m = 1. Component (B): represented by the general formula R ³ _m SiX _4-m (I) (wherein R ³ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms). , M is an integer of 0 to 3, and X is a hydrolyzable group) hydrolyzable organosilane is added in an organic solvent, water or a mixed solvent thereof to water per 1 mol equivalent of the hydrolyzable group (X). 0.
An organosilane oligomer partially hydrolyzed under the condition of using 001 to 0.5 mol (hereinafter, this may be referred to as "organosilane oligomer (B)"). Component (C): represented by an average composition formula R ⁴ _a Si (OH) _b O _{(4-ab) / 2} (II) (wherein R ⁴ is the same or different and is substituted or unsubstituted and has 1 to 1 carbon atoms). 8 is a monovalent hydrocarbon group, and a and b are 0.2 ≦ a ≦ 2 and 0.0001 ≦ b ≦, respectively.
3, a number satisfying the relationship of a + b <4), and a polyorganosiloxane containing a silanol group in the molecule (hereinafter,
This may be referred to as "(silanol group-containing) polyorganosiloxane (C)"). Component (D): Silica (hereinafter, this may be referred to as "silica (D)"). Component (E): curing catalyst (hereinafter, this may be referred to as "curing catalyst (E)").

The component (B) of the silicone resin (2) is added to the organic solvent, water or a mixed solvent thereof in the component (D).
In the colloidal silica in which the components are dispersed, the hydrolyzable organosilane is partially hydrolyzed under the condition of using 0.001 to 0.5 mol of water per 1 mol equivalent of the hydrolyzable group (X). The component (D) is 3 to 3 relative to the total solid content of the component (B) and the component (D).
It is preferably a silica-dispersed organosilane oligomer containing 95% by weight.

When the silicone resin (2) is used as the silicone resin, the silane-modified surfactant is contained in an amount of 0 per 1 mol of total hydrolyzable organosilane which is a raw material of the component (B) when the component (B) is prepared. It is preferable that it is contained in the coating material by adding it in an amount of 0.001 to 3 mol. The hydrophilic inorganic coating material of the present invention can also contain an optical semiconductor, if necessary.

The hydrophilic inorganic coating material of the present invention, if necessary,
An antistatic agent can also be included. The hydrophilic inorganic coating material of the present invention may also contain an ultraviolet absorber, if necessary. The hydrophilic inorganic coating material of the present invention, if necessary,
Colorants can also be included.

The hydrophilic coated article of the present invention has the following properties:
The coating layer comprises a coating and cured coating of the hydrophilic inorganic coating material of the present invention. The base material is an inorganic base material, an organic base material, an inorganic-organic composite base material, or a coating base having at least one layer of an inorganic material coating and / or at least one layer of an organic material coating on the surface of any of these base materials. It is preferable that each material is selected from the group consisting of individual materials, composite materials obtained by combining at least two of these materials, and laminated materials obtained by laminating at least two of these materials.

The substrate is metal, glass, hollow, ceramics, cement, concrete, wood, wood, plastic, inorganic fiber reinforced plastic, or at least one of these substrates on the surface. Each single material of the coated substrate having a layer of inorganic coating and / or at least one organic coating, a composite material of at least two of these, and at least two of these laminated More preferably, it is selected from the group consisting of the following laminated materials.

The coating film on the surface of the coated substrate may be a primer layer.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The hydrophilic inorganic coating material of the present invention contains a silicone resin as a main component. This silicone resin is used as a film forming component. As the silicone resin, a point that a crosslinking reaction with a silane-modified surfactant is possible, a point that it does not deteriorate with time even when an additive such as an optical semiconductor described later is mixed, and a weather resistance, hardness and resistance of a coating film obtained are obtained. From the viewpoint of cracking property, the silicone resin (1) containing the component (A) is preferable, and it is capable of undergoing a crosslinking reaction with a silane-modified surfactant and is mixed with an additive such as an optical semiconductor described later. In view of not being deteriorated with time even if it is allowed to stand, room temperature (normal temperature) curability, and weather resistance, hardness, crack resistance and the like of the obtained coating film, the above (B), (C), (D) and The silicone resin (2) containing the component (E) is preferable.
Among these silicone resins (1) and (2), the silicone resin (1) is particularly preferable in that a coating film having higher hardness can be obtained and the pot life is long.

In the following, first, the silicone resin (1)
Each component of will be described. As the raw material of the component (A) contained in the silicone resin (1), that is, the organosiloxane (A), the silicon compound (A ₁ ) to
A hydrolyzable mixture containing (A ₃ ) is used. The silicon compounds (A ₁ ) to (A ₃ ) other than the colloidal silica can be generally represented by the general formula R ² _p Si (OR ¹ ) _4-p (III) (here, R ¹ , R ² Represents a monovalent hydrocarbon group, and p is an integer of 0 to 2).

R ² is not particularly limited, but examples thereof include a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. Specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group,
Alkyl groups such as heptyl group, octyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group; aralkyl groups such as 2-phenylethyl group, 2-phenylpropyl group, 3-phenylpropyl group; phenyl group, tolyl group, etc. Aryl group; alkenyl group such as vinyl group and allyl group; chloromethyl group, γ-chloropropyl group, 3,3
Halogen-substituted hydrocarbon group such as 3-trifluoropropyl group; γ-methacryloxypropyl group, γ-glycidoxypropyl group, 3,4-epoxycyclohexylethyl group, γ-mercaptopropyl group, etc. Can be illustrated. Among these, an alkyl group having 1 to 4 carbon atoms and a phenyl group are preferable from the viewpoint of ease of synthesis or availability.

Further, R ¹ is not particularly limited, but, for example, one containing an alkyl group having 1 to 4 carbon atoms as a main raw material is used. In particular, tetramethoxysilane, tetraethoxysilane and the like can be exemplified as p = 0 tetraalkoxysilane, and methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane can be exemplified as p = 1 organotrialkoxysilane. , Phenyltrimethoxysilane, phenyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, and the like. Examples of the p = 2 diorganodialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane.

These R ¹ and R ² may be the same or different among the silicon compounds (A ₁ ) to (A ₃ ). The organosiloxane (A) is obtained, for example, by diluting the hydrolyzable mixture with a suitable solvent, and adding water as a curing agent and a catalyst (for example, hydrochloric acid, acetic acid, halogenated silane, chloroacetic acid, citrate, etc.) as necessary. Acid, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, toluenesulfonic acid, organic acids such as oxalic acid, and one or more kinds of inorganic acids) and the like. Add the required amount (heat as necessary (for example, 40 to 10
It may be carried out at 0 ° C.), or a hydrolysis and polycondensation reaction is performed to form a prepolymer. At that time, the weight average molecular weight (Mw) of the obtained prepolymer (hydrolyzed polycondensate) was 9 in terms of polystyrene.
It is adjusted to be 00 or more, preferably 1000 or more. Molecular weight distribution of prepolymer (weight average molecular weight (M
When w)) is less than 900, the curing shrinkage during the condensation polymerization of the silicone resin (1) is large and cracks are likely to occur in the coating film after curing.

The amount of the raw materials (A ₁ ) to (A ₃ ) used in preparing the organosiloxane (A) is 0.1 to 20 moles (A ₂ ) of 1 mole of (A ₁ ) (preferably Is 0.1
-18 mol, more preferably 0.1-15 mol), (A
₃ ) The ratio is 0.6 mol or less (preferably 0.4 mol or less, more preferably 0.3 mol or less). If the amount of (A ₂ ) used is less than the above range, or if the amount of (A ₃ ) used is more than the above range, the desired hardness of the cured coating cannot be obtained (the hardness decreases). . Also,
If the amount of (A ₂ ) used is more than the above range, the cross-linking density of the cured coating becomes too high and the hardness becomes too high, which causes the problem that cracks are likely to occur.

As the raw material (A ₂ ), the above-mentioned general formula Si is used.
Only one or both of the silicon compound represented by (OR ¹ ) ₄ and colloidal silica are used. Silica has the effect of increasing the hardness of the coated and cured film of the hydrophilic inorganic paint and improving the smoothness and crack resistance.
The colloidal silica that can be used is not particularly limited, but for example, water-dispersible or non-aqueous organic solvent-dispersed colloidal silica such as alcohol can be used.
Generally, such colloidal silica contains 20 to 50% by weight of silica as a solid content, and the amount of silica can be determined from this value. When water-dispersible colloidal silica is used, water present as a component other than the solid content can be used as a curing agent as described later. 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, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, etc. can also be used.

When colloidal silica is used as at least a part of the raw material (A ₂ ), the amount of colloidal silica contained in the above-mentioned used amount of (A ₂ ) is a molar amount as a silica component. If necessary, silica may be added to and mixed with the organosiloxane (A) prepared without using silica, or even if silica is used for the preparation of organosiloxane (A), If desired, silica may be additionally mixed with the organosiloxane (A). As silica that can be used in those cases,
There is no particular limitation, and known ones can be used. Further, the form of silica at that time is not particularly limited, and may be, for example, a powder form or the colloidal silica form.

Water is used as a curing agent used in the hydrolysis polycondensation reaction of the above-mentioned hydrolyzable mixture which is a raw material of the organosiloxane (A). Water is preferably 0.01 to 3.0 mol, and 0.3 to 1 mol equivalent of the OR ¹ group contained.
1.5 mol is more preferable. Examples of the diluting solvent used in the hydrolysis polycondensation reaction of the hydrolyzable mixture include methanol, ethanol, isopropanol, n-butanol, and the like, which are described above as the dispersion solvent of colloidal silica.
Lower aliphatic alcohols such as isobutanol; ethylene glycol, ethylene glycol monobutyl ether,
Examples thereof include ethylene glycol derivatives such as ethylene glycol monoethyl ether acetate; diethylene glycol derivatives such as diethylene glycol and 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, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, etc. can be exemplified.

The pH of the organosiloxane (A) is preferably adjusted within the range of 3.8-6.
If the pH is within this range, within the above molecular weight range,
The organosiloxane (A) can be stably used. If the pH is out of this range, the stability of the organosiloxane (A) is poor, and the usable period from the time of coating preparation is limited. Here, the pH adjusting method is not particularly limited, but, for example, when the raw material of the organosiloxane (A) is mixed and the pH is less than 3.8, for example, a basic reagent such as ammonia is used. It may be used to adjust the pH within the above range, and when the pH exceeds 6, it may be adjusted using an acidic reagent such as hydrochloric acid. Further, depending on the pH, the reaction does not proceed to the contrary with the molecular weight being small, and when it takes time to reach the molecular weight range, the organosiloxane (A) may be heated to accelerate the reaction. The pH may be lowered with a reagent to proceed the reaction, and then the pH may be returned to a predetermined pH with a basic reagent.

The silicone resin (1) does not need to contain a curing catalyst when it is cured by heating, but by promoting the condensation reaction of the component (A), it accelerates the heating and curing of the coating film, or the coating film at room temperature. A curing catalyst can be further included, if necessary, for the purpose of curing at a low temperature including. The curing catalyst is not particularly limited, but examples thereof include alkyl titanates; carboxylic acid metal salts such as tin octylate, dibutyltin dilaurate and dioctyltin dimaleate; dibutylamine-2-hexoate, dimethylamine acetate, ethanolamine acetate. Amine salts such as; carboxylic acid quaternary ammonium salts such as tetramethylammonium acetate; amines such as tetraethylpentamine; N-β-aminoethyl-γ-aminopropyltrimethoxysilane; N-β-aminoethyl-γ
-Amine-based silane coupling agents such as aminopropylmethyldimethoxysilane; acids such as p-toluenesulfonic acid, phthalic acid, hydrochloric acid; aluminum compounds such as aluminum alkoxides and aluminum chelates; lithium acetate, potassium acetate, lithium formate, sodium formate , Alkali metal salts such as potassium phosphate, potassium hydroxide; titanium compounds such as tetraisopropyl titanate, tetrabutyl titanate, titanium tetraacetylacetonate; halogenated silanes such as methyltrichlorosilane, dimethyldichlorosilane, trimethylmonochlorosilane, etc. Is mentioned. But besides these,
There is no particular limitation as long as it is effective for promoting the condensation reaction of the component (A).

When the silicone resin (1) also contains a curing catalyst, the amount thereof is preferably 10% by weight or less, based on the total solid content of the organosiloxane (A) in terms of the total condensation compound,
It is more preferably 8% or less. If it exceeds 10% by weight, the storage stability of the hydrophilic inorganic coating may be impaired. When the silicone resin contained in the hydrophilic inorganic paint is the silicone resin (1), the hydrophilic inorganic paint is
By heating at a low temperature in the presence of a curing catalyst or leaving it at room temperature, the hydrolyzable groups of the component (A) undergo a condensation reaction to form a cured coating film. Therefore,
Such a hydrophilic inorganic coating is hardly affected by humidity even when it is cured at room temperature. Further, if heat treatment is performed, a condensation reaction can be promoted to form a cured film without using a curing catalyst.

Next, each component of the silicone resin (2) will be described. The component (B) contained in the silicone resin (2), that is, the organosilane oligomer (B)
Is a main component of a base polymer having a hydrolyzable group (X) as a functional group that is involved in a curing reaction when forming a cured film of a hydrophilic inorganic paint. This is, for example, an organic solvent or water (a mixed solvent of an organic solvent and water may be used).
In addition, one or more of the hydrolyzable organosilane represented by the general formula (I) is added, and water (water previously contained in the solvent and / or water separately added) is added to the above-mentioned water. Water 0.001 to 1 mol equivalent of decomposable group (X)
It can be obtained by partially hydrolyzing the hydrolyzable organosilane under the condition of using 0.5 mol.

As the group R ³ in the hydrolyzable organosilane represented by the above general formula (I), the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms is particularly preferable. Although not limited, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; 2
-Aralkyl groups such as phenylethyl group, 2-phenylpropyl group and 3-phenylpropyl group; aryl groups such as phenyl group and tolyl group; alkenyl groups such as vinyl group and allyl group; chloromethyl group, γ-chloropropyl group , 3,
Halogen-substituted hydrocarbon groups such as 3,3-trifluoropropyl group; γ-methacryloxypropyl group, γ-glycidoxypropyl group, 3,4-epoxycyclohexylethyl group, γ-mercaptopropyl group and other substituted hydrocarbon groups A group etc. can be illustrated. Among these, an alkyl group having 1 to 4 carbon atoms and a phenyl group are preferable from the viewpoint of ease of synthesis or availability.

In the general formula (I), the hydrolyzable group X is not particularly limited, but examples thereof include an alkoxy group, an acetoxy group, an oxime group, an enoxy group, an amino group, an aminoxy group and an amide group. To be Among these, the alkoxy group is preferable because it is easily available and the organosilane oligomer (B) is easily prepared.

Specific examples of the hydrolyzable organosilane include mono-, di-, tri-, and tetra-functional alkoxysilanes in which m in the general formula (I) is an integer of 0 to 3. , Acetoxysilanes, oxime silanes,
Examples thereof include enoxysilanes, aminosilanes, aminoxysilanes, amidosilanes and the like. Among these, alkoxysilanes are preferable because they are easily available and the organosilane oligomer (B) is easily prepared.

Among the alkoxysilanes, m = 0
Examples of the tetraalkoxysilane include tetramethoxysilane and tetraethoxysilane, and examples of the m = 1 organotrialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, and phenyltrimethoxysilane. ,
Examples include phenyltriethoxysilane and 3,3,3-trifluoropropyltrimethoxysilane. Further, as the diorganodialkoxysilane of m = 2,
Examples thereof include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane. Triorganoalkoxysilanes with m = 3 include trimethylmethoxysilane, trimethylethoxysilane, and trimethylisopropoxysilane. , Dimethylisobutylmethoxysilane, and the like. Furthermore, the organosilane compound generally called a silane coupling agent is also included in the alkoxysilanes.

Of these hydrolyzable organosilanes represented by the general formula (I), 50 mol% or more (preferably 60 mol% or more, more preferably 70 mol% or more)
Is a trifunctional compound represented by m = 1. This is,
If it is less than 50 mol%, sufficient coating film hardness cannot be obtained, and the dry curing property of the coating film tends to be poor. The amount of water used when preparing the organosilane oligomer (B) is
As described above, 0.001 to 0.5 per mol equivalent of the hydrolyzable group (X) possessed by the hydrolyzable organosilane.
It is within the range of moles, preferably within the range of 0.01 to 0.4 moles. When the amount of water used is less than 0.001 mol,
Sufficient partial hydrolyzate cannot be obtained, and if it exceeds 0.5 mol, the stability of the partial hydrolyzate becomes poor. Here, the amount of water used in the partial hydrolysis reaction of the hydrolyzable organosilane is the amount of water added separately when only the organic solvent is used as the reaction solvent, and only water or the organic solvent is used as the reaction solvent. When a mixed solvent of a solvent and water is used,
It is the amount of water previously contained in at least the reaction solvent among water previously contained in the reaction solvent and water added separately. It is not necessary to add water separately if the amount of water is only the water previously contained in the reaction solvent and the amount used is sufficient, but the amount of water was previously contained in the reaction solvent. When water alone is not enough to reach the above usage amount, it is necessary to separately add water until the above usage amount is reached. In this case, the amount of water used is the total amount of water previously contained in the reaction solvent and water added separately. In addition, even when the amount of water previously contained in the reaction solvent is sufficient for the use amount, water may be added separately, and in that case, the amount of water used is not included in the reaction solvent beforehand. The total amount of water that was added and the water that was added separately. However, water is added separately so that this total amount does not exceed the above upper limit (0.5 mol per 1 mol equivalent of the hydrolyzable group (X)).

The method for partially hydrolyzing the hydrolyzable organosilane is not particularly limited, and for example, the hydrolyzable organosilane and the reaction solvent may be mixed (whether the reaction solvent contains no water or If the required amount is not included, add water here). At that time, the partial hydrolysis reaction proceeds at room temperature, but in order to accelerate the partial hydrolysis reaction, if necessary, heating (for example, 60 to
100 ° C.) or a catalyst may be used. The catalyst is not particularly limited, but for example, hydrochloric acid, acetic acid, halogenated silane, chloroacetic acid, citric acid,
One or more of organic acids such as benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, toluenesulfonic acid and oxalic acid, and inorganic acids can be used. .

The organosilane oligomer (B) has its pH adjusted to obtain its performance stably over a long period.
Preferably 2.0 to 7.0, more preferably 2.5 to
It is better to set it to 6.5, and more preferably to 3.0 to 6.0. When the pH is out of this range, the performance sustainability of the component (B) is remarkably reduced particularly under the condition that the amount of water used is 0.3 mol or more per mol equivalent of the hydrolyzable group (X). When the pH of the component (B) is outside the above range, if it is on the acidic side of this range, the pH may be adjusted by adding a basic reagent such as ammonia or ethylenediamine. If it is on the basic side, The pH may be adjusted using an acidic reagent such as hydrochloric acid, nitric acid or acetic acid. However, the adjusting method is not particularly limited.

The component (C) contained in the silicone resin (2), that is, the silanol group-containing polyorganosiloxane (C), is the base polymer having a hydrolyzable group as a functional group involved in the curing reaction. It is a cross-linking agent for forming a three-dimensional cross-link in the cured film by condensation reaction with the component), and is a component effective in absorbing the strain due to the curing shrinkage of the component (B) and preventing the occurrence of cracks.

As R ⁴ in the average composition formula (II) representing the silanol group-containing polyorganosiloxane (C),
It is not particularly limited, and examples thereof include the same ones as R ³ in the above formula (I), but preferably an alkyl group having 1 to 4 carbon atoms, a phenyl group, a vinyl group, a γ-glycidoxypropyl group, Substituted hydrocarbon groups such as γ-methacryloxypropyl group, γ-aminopropyl group and 3,3,3-trifluoropropyl group, more preferably methyl group and phenyl group. In the formula (II), a and b are numbers satisfying the above relationship, and a is less than 0.2 or b
When it exceeds 3, there is a disadvantage that a cured coating film of the hydrophilic inorganic coating material is cracked. Also, a exceeds 2 and 4
In the following cases or when b is less than 0.0001, curing does not proceed well.

The silanol group-containing polyorganosiloxane (C) is not particularly limited, but for example,
Methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane,
Alternatively, it can be obtained by hydrolyzing one or a mixture of two or more corresponding alkoxysilanes with a large amount of water by a known method. When the silanol group-containing polyorganosiloxane (C) is hydrolyzed by a known method using an alkoxysilane, a small amount of unhydrolyzed alkoxy groups may remain. That is, a polyorganosiloxane in which a silanol group and an extremely small amount of an alkoxy group coexist may be obtained, but such a polyorganosiloxane may be used in the present invention.

The component (D) of the silicone resin (2), that is, silica (D), has the effects of increasing the hardness of the coated and cured coating of the hydrophilic inorganic coating material and improving the smoothness and crack resistance. The silica (D) is not particularly limited, and known silica can be used. The silica (D) is not particularly limited, but it may be introduced into the paint by dispersing it in the form of colloidal silica in the reaction solvent used when preparing the component (B). It is preferable in terms of film forming property and simplification of the process. However, it is not limited to this. For example, after mixing silica (D) with the component (B) obtained by preparing without silica (D), the resulting mixture may be introduced into a coating material, or silica (D) may be ( It may be introduced into the paint separately from the component B).

The form of silica (D) when it is introduced into the paint is not particularly limited, and may be, for example, a powder form or a colloidal silica form. The colloidal silica is not particularly limited, but for example, the above-mentioned ones as the raw material (A ₂ ) of the organosiloxane (A) can be used. When using the water-dispersible colloidal silica, the water present as a component other than the solid content in the colloidal silica should be used for the hydrolysis of the hydrolyzable organosilane that is the raw material of the component (B). It can be used (added to the amount of water used during hydrolysis) and can be used as a curing agent for hydrophilic inorganic coatings.

Silica (D) has the above-mentioned effects, but if the blending amount is too large, the cured coating of the hydrophilic inorganic coating may become too hard and may cause cracks in the coating. . Therefore, the silica (D) is preferably 3 to 95% by weight based on the total solid content of the component (B),
More preferably 5 to 90% by weight, still more preferably 7 to
It is contained within the range of 85% by weight. If the content is less than 3% by weight, the desired coating hardness may not be obtained. On the other hand, if it exceeds 95% by weight, cracks are likely to occur.

The above-mentioned component (E) contained in the silicone resin (2), that is, the curing catalyst (E), accelerates the condensation reaction between the above-mentioned components (B) and (C) to form a coating film of a hydrophilic inorganic paint. It is a curing component. The curing catalyst (E) is not particularly limited, but examples thereof include alkyl titanates; carboxylic acid metal salts such as tin octylate, dibutyltin dilaurate and dioctyltin dimaleate; dibutylamine-2-hexoate, dimethylamine acetate, Amine salts such as ethanolamine acetate; carboxylic acid quaternary ammonium salts such as tetramethylammonium acetate; amines such as tetraethylpentamine; N
Amine-based silane coupling agents such as -β-aminoethyl-γ-aminopropyltrimethoxysilane and N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane; acids such as p-toluenesulfonic acid, phthalic acid and hydrochloric acid Aluminum compounds such as aluminum alkoxide and aluminum chelate; alkali metal salts such as lithium acetate, lithium formate, sodium formate, potassium phosphate, potassium hydroxide; tetraisopropyl titanate,
Titanium compounds such as tetrabutyl titanate and titanium tetraacetylacetonate; halogenated silanes such as methyltrichlorosilane, dimethyldichlorosilane and trimethylmonochlorosilane. However, other than these, there is no particular limitation as long as it is effective in promoting the condensation reaction between the component (B) and the component (C).

The mixing ratio of the component (B) and the component (C) in the silicone resin (2) is not particularly limited,
For example, in terms of total condensation compound equivalent solid content,
With respect to 100 parts by weight of the total of the components (B) and (C),
(B) component 0.5 to 99.5 parts by weight, (C) component 99.
5 to 0.5 parts by weight is preferable, and the component (B) is 2.5 to 9
7.5 parts by weight, 97.5 to 2.5 parts by weight of the component (C) are more preferable, 5 to 95 parts by weight of the component (B), component 9 of the (C)
More preferably 5 to 5 parts by weight. When the amount of the component (B) is less than 0.5 parts by weight (the amount of the component (C) exceeds 99.5 parts by weight), the room temperature curability tends to be poor, and sufficient coating hardness tends not to be obtained. On the other hand, the component (B) exceeds 99.5 parts by weight (the component (C) is less than 0.5 parts by weight).
If so, the curability may be unstable, and a good coating film may not be obtained.

The blending ratio of the component (E) in the silicone resin (2) is not particularly limited, but is, for example, (B).
It is preferably within the range of 0.0001 to 10 parts by weight, and more preferably 0.0005 to 8 parts by weight, based on 100 parts by weight of the total solid content of the component and the total solid content of the component (C). It is in the range of parts by weight, and more preferably in the range of 0.0007 to 5 parts by weight. If the compounding amount of (E) is less than 0.0001 parts by weight, the room temperature curability is lowered,
Further, there is a tendency that sufficient coating hardness cannot be obtained. If it exceeds 10 parts by weight, the heat resistance and weather resistance of the cured coating may be deteriorated, or the hardness of the cured coating may be too high and cracks may occur.

When the silicone resin contained in the hydrophilic inorganic coating material is the silicone resin (2), the hydrophilic inorganic coating material has the hydrolyzable group contained in the organosilane oligomer (B) and the polyorganosiloxane (C). In the presence of the curing catalyst (E) in the presence of the curing catalyst (E), the silanol group undergoes a condensation reaction by being left at room temperature or heated at a low temperature to form a cured film. Therefore, such a hydrophilic inorganic coating is hardly affected by humidity even when it is cured at room temperature. Further, the cured film can be formed by promoting the condensation reaction by heat treatment.

The silane-modified surfactant having a reactive group at the end contained in the hydrophilic inorganic coating material of the present invention is used for imparting hydrophilicity to the surface of the coating film. The silane-modified surfactant is preferably one that undergoes a crosslinking reaction with a silicone resin component, and is not particularly limited, but for example, the compound represented by the general formula (a) can be used. ..

In the general formula (a), the hydrophilic group R⁰As a special
But not limited to, for example, -COOH, -OSO
₃ ^-, -SO₃= N =⁺Ionic such as -OH
  , Non-ionic ones such as polyoxyethylene chains
To be Ionic is H⁺, Na⁺, K⁺, Ca
²⁺, NH_Four ⁺, Organic ammonium (eg HOCH ₂
CH₂NH₃ ⁺Etc) cations, Cl^-, Br^-Etc.
Only when paired with a counterion such as anion, is ionic strength strong.
Changes. Non-ionic ones include the number of -OH groups and
The hydrophilicity changes depending on the length of the polyoxyethylene chain, etc.
It

In the general formula (a), the hydrolyzable group X is not particularly limited, but examples thereof include an alkoxy group, an acetoxy group, an oxime group, an enoxy group, an amino group, an aminoxy group and an amide group. To be Among these, an alkoxy group is preferable from the viewpoint of easiness of reaction control with the silicone resin (particularly the component (A) or the component (B)).

The timing of the addition of the silane-modified surfactant is not particularly limited, but the base polymer of the silicone resin (for example, the component (A) in the case of the silicone resin (1) and the () in the case of the silicone resin (2)). It is preferable to add the silane-modified surfactant during the preparation of the component (B), because the silane-modified surfactant can be easily and reliably incorporated and fixed in the matrix of the silicone resin by a crosslinking reaction with the silicone resin. However, the present invention is not limited to this, and for example, after mixing the silane-modified surfactant with the silicone resin obtained by preparing without the silane-modified surfactant, the resulting mixture may be introduced into a paint, Alternatively, the silane-modified surfactant may be introduced into the coating separately from the silicone resin.

The content of the silane-modified surfactant in the hydrophilic inorganic coating material is not particularly limited. For example, when the silicone resin (1) is used as the silicone resin, the total amount of the raw materials of the component (A) is used. Per mol of silicon compound (excluding colloidal silica), preferably 0.0
25 to 1 mol, more preferably 0.03 to 0.8 mol,
The ratio is more preferably 0.035 to 0.6 mol, and when the silicone resin (2) is used as the silicone resin, it is preferably 1 mol per total hydrolyzable organosilane which is a raw material of the component (B). 0.01 ~
The amount is 3 mol, more preferably 0.015 to 2 mol, still more preferably 0.02 to 1 mol. When the amount of the silane-modified surfactant is less than the above range, a coating film showing high hydrophilicity may not be obtained from the initial stage after film formation, and when it is more than the above range, the silane-modified interface The activator becomes a curing inhibitor in the silicone resin, and there is a possibility that sufficient coating film hardness cannot be obtained.

The hydrophilic inorganic coating material of the present invention, if necessary,
It may also contain an optical semiconductor. 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, cadmium oxide, and oxide. In addition to metal oxides such as copper, vanadium oxide, niobium oxide, tantalum oxide, manganese oxide, cobalt oxide, rhodium oxide, nickel oxide and rhenium oxide, strontium titanate has a photocatalytic action as well as a curing promoting action. preferable. Among these, the metal oxide,
It is preferable in terms of practical ease of use, and among the metal oxides, titanium oxide is particularly preferable in terms of its photocatalytic performance, curing promotion performance, safety, availability, and cost. When titanium oxide is used as an optical semiconductor,
The photocatalytic performance and the curing acceleration performance are the strongest when the crystal type is anatase type (anatase type).
Moreover, it is preferable in that it develops for a long period of time and the photocatalytic performance and the curing acceleration performance are developed in a shorter time.

When transparency of the coating film is required, the average primary particle diameter of the optical semiconductor is preferably 50 μm or less, more preferably 5 μm or less, and 0.5 μm.
It is more preferably m or less. The optical semiconductors may be used alone or in combination of two or more.

The optical semiconductor may be in any form as long as it can be dispersed in the coating material such as powder, fine particle powder, solution-dispersed sol particles and the like. Curing progresses in a shorter time, which is convenient for use. When a sol is used, the dispersion medium may be water or an organic solvent, but the organic solvent is preferable from the viewpoint of coating preparation.

Further, the raw material of the optical semiconductor is not limited as long as it finally shows the properties of the optical semiconductor. It is known that an optical semiconductor emits active oxygen (photocatalytic property) when irradiated with ultraviolet rays. Since active oxygen can oxidize and decompose organic substances, its characteristics are utilized to make use of the characteristics of carbon-based contaminant components (for example, carbon fractions contained in exhaust gas of automobiles,
Self-cleaning effect of decomposing tobacco tar and the like; Deodorizing effect of decomposing 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; The effect and the like can be obtained. When a coating film containing a photo-semiconductor is exposed to ultraviolet rays, the photo-semiconductor photocatalytically converts water into hydroxyl radicals, and the hydroxyl radicals repel water. By decomposing (the substance contained therein), the hydrophilicity (wettability) of the coating film with respect to water is further improved, and the antifogging property and the antifouling property due to washing with rainwater are further improved.

Further, there is an antistatic function due to the photocatalytic action of the optical semiconductor, and this function also provides an antifouling effect. For example, when a coating film of a hydrophilic inorganic coating material containing an optical semiconductor is irradiated with light, the surface resistance value of the coating film is lowered by the action of the optical semiconductor contained in the coating film, so that the antistatic effect is exhibited and the coating film is coated. The surface is less likely to get dirty. Furthermore, when the above-mentioned metal oxide and strontium titanate, which have not only a photocatalytic action but also a curing promoting action, are used as the optical semiconductor, the curing promoting action increases the curing rate and the weather resistance of the film. It has not yet been clearly confirmed by what mechanism the surface resistance value of the coating film decreases or the curing of the coating film is accelerated when the coating film containing an optical semiconductor is irradiated with light. It is considered that this is due to the action of electrons and holes generated by.

A metal supported on the surface of the optical semiconductor is preferable because the photocatalytic effect of the optical semiconductor is further enhanced. The mechanism has not yet been clearly confirmed, but by supporting a metal on the surface of the photosemiconductor, charge separation of the photosemiconductor is promoted, and the disappearance of electrons and holes generated by the charge separation is established. It seems that getting smaller is related.

Examples of the metal that may be supported on the surface of the optical semiconductor include silver, copper, iron, nickel, zinc, platinum,
Gold, palladium, cadmium, cobalt, rhodium, ruthenium and the like are preferable in terms of further promoting charge separation of the optical semiconductor. The supported metal may be only one kind or two or more kinds. The amount of the metal carried is not particularly limited, but is preferably 0.1 to 10% by weight, and more preferably 0.2 to 5% by weight based on the photosemiconductor. If the loading amount is less than 0.1% by weight, the loading effect tends not to be sufficiently obtained, and if the loading amount exceeds 10% by weight, the effect does not increase so much, and conversely, discoloration or performance deterioration may occur. Problems tend to occur.

The method of supporting the metal is not particularly limited, but examples thereof include an immersion method, an impregnation method, and a photoreduction method. Moreover, you may use the clay crosslinked body which carry | supported the optical semiconductor between layers. By introducing the photo-semiconductor between the layers, the photo-semiconductor is supported on the fine particles and the photocatalytic performance is improved. In the hydrophilic inorganic coating material, the compounding amount of the optical semiconductor is not particularly limited. In the case where the metal is not supported on the surface of the optical semiconductor, preferably 5 to 500 parts by weight,
The amount is more preferably 10 to 100 parts by weight, and preferably 2 to 2 when a metal is supported on the surface of the optical semiconductor.
The amount is 00 parts by weight, more preferably 5 to 100 parts by weight.
If the amount of the photo-semiconductor compounded is less than the above range, it tends to be difficult to obtain a sufficient photocatalytic function, and if it is more than the above range, the coating film performance tends to deteriorate such that cracks are likely to occur. .. In addition, when the metal is supported on the surface of the optical semiconductor, the compounding amount of the optical semiconductor is an amount not including the supported metal.

The hydrophilic inorganic coating material of the present invention, if necessary,
It is also possible to include antistatic agents. The antistatic agent is not particularly limited, but for example, tin oxide,
Conductive metal oxide fine particles such as antimony oxide, antimony oxide-zinc oxide composite, antimony oxide-tin oxide composite (ATO), indium oxide-tin oxide composite (ITO); copper powder, iron powder, nickel powder, Examples thereof include fine metal particles such as silver powder, gold powder and platinum powder; conductive carbon such as carbon black and carbon fiber. It is desirable that each particle diameter of the conductive metal oxide fine particles, the metal fine particles and the conductive carbon is small in order not to impair the smoothness of the cured coating film, and for example, 10 μm or less is preferable. The shapes of the conductive metal oxide fine particles, the metal fine particles, and the conductive carbon are not particularly limited to particles, and may be needle-like, fiber-like or the like as long as the smoothness of the cured coating film is not impaired. Absent. Further, the conductive metal oxide fine particles, the amount of the metal fine particles and the conductive carbon is different depending on the conductivity specific to each material, in order not to impair the strength of the cured coating film, the total condensation compound in the total amount of the coating Converted solid content 10
It is preferably 1 to 200 parts by weight, more preferably 10 to 150 parts by weight, relative to 0 parts by weight. The hydrophilic inorganic coating material can have high conductivity by containing the antistatic agent.

The hydrophilic inorganic coating material of the present invention, if necessary,
It is also possible to contain UV absorbers. The ultraviolet absorber is not particularly limited, and examples thereof include inorganic UV absorbers such as cerium oxide, titanium oxide, zinc oxide, iron oxide, vanadium oxide, lead oxide, and antimony oxide, as well as salicylic acid-based substances such as phenyl salicylate. Examples include UV absorbers, benzophenone-based UV absorbers such as hydroxybenzophenone, benzotriazole-based UV absorbers such as hydroxymethylphenylbenzotriazole, and organic UV absorbers such as cyanoacrylate-based UV absorbers such as ethylhexyl cyanodiphenyl acrylate. . The particle size of the inorganic ultraviolet absorber is preferably such that the smoothness and strength of the cured coating film are not impaired, and for example, 10 μm or less is preferable. The amount of UV absorber blended is
Although it depends on the UV absorption capacity unique to each material, it is desirable that the smoothness and strength of the cured coating film are not impaired, and in order to obtain sufficient UV absorption capacity, conversion to total condensation compounds in the total amount of paint is required. The solid content is preferably 10 to 200 parts by weight, more preferably 2 to 100 parts by weight.
0 to 150 parts by weight. The hydrophilic inorganic coating material can have a high ultraviolet blocking effect by containing an ultraviolet absorber, and when the base of the coating film is an organic material, it prevents the base from being deteriorated by ultraviolet rays.

The hydrophilic inorganic coating material of the present invention, if necessary,
Toning can be performed by further containing a coloring agent such as a pigment or a dye. The pigment that can be used is not particularly limited, for example, carbon black, quinacridone, naphthol red, cyanine blue, cyanine green,
Organic pigments such as Hansa Yellow; inorganic pigments such as titanium oxide, barium sulfate, rouge, complex metal oxides, etc. are preferable, and one kind or a combination of two or more kinds selected from these groups may be used. The dispersion of the pigment is not particularly limited, and a usual method such as a method of directly dispersing the pigment powder with a dyno meal, a paint shaker, or the like may be used. At that time, it is possible to use a dispersant, a dispersion aid, a thickener, a coupling agent and the like. The amount of the pigment added is not particularly limited because the hiding property varies depending on the type of the pigment, but, for example, the total condensation compound-equivalent solid content in the total amount of the coating material is 100.
The amount is preferably 5 to 80 parts by weight, more preferably 10 to 70 parts by weight, based on parts by weight. When the amount of the pigment added is less than 5 parts by weight, the hiding property tends to deteriorate, and when it exceeds 80 parts by weight, the smoothness of the coating film may deteriorate.

The dye that can be used is not particularly limited, and examples thereof include azo type, anthraquinone type, indicoid type, sulfide type, triphenylmethane type, xanthene type, alizarin type, acridine type, quinone imine type,
Examples thereof include thiazole dyes, methine dyes, nitro dyes, and nitroso dyes. One kind or two or more kinds selected from these groups may be used in combination. The amount of the dye added is not particularly limited because the hiding property varies depending on the type of the dye, but for example, it is preferably 5 to 100 parts by weight of the total condensation compound-equivalent solid content in the total amount of the coating material.
The amount is 80 parts by weight, more preferably 10 to 70 parts by weight.
If the amount of the dye added is less than 5 parts by weight, the hiding property tends to deteriorate, and if it exceeds 80 parts by weight, the smoothness of the coating film may deteriorate.

A leveling agent, metal powder, glass powder,
An antibacterial agent, an antioxidant and the like may be contained in the hydrophilic inorganic coating material as long as the effects of the present invention are not adversely affected. The hydrophilic inorganic coating composition can be used by diluting it with various organic solvents, if necessary, from the viewpoint of easy handling, or may be diluted with the same organic solvent. The type of organic solvent can be appropriately selected according to the type of monovalent hydrocarbon group possessed by each component of the silicone resin, the size of the molecular weight of each component of the silicone resin, or the like. The organic solvent is not particularly limited, but examples thereof include lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol, and isobutanol; ethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether acetate. Ethylene glycol derivatives such as; ethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and toluene, xylene, hexane, heptane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, diacetone alcohol, etc. , Or one or more selected from the group consisting of these can be used. The dilution ratio with the organic solvent is not particularly limited, and the dilution ratio may be appropriately determined as necessary.

The method for producing the hydrophilic inorganic coating material is not particularly limited, and the respective components may be mixed using a usual method and apparatus. Regarding the form of each component when it is introduced into the paint, it may be a liquid itself, a solution dissolved in a solvent, a liquid such as a dispersion liquid dispersed in a dispersion medium, or a solid state such as powder. In any case, it is not particularly limited. When each component is introduced in the form of a solution or dispersion, the solvent or dispersion medium thereof is, for example, water, the above-mentioned organic solvent, or
Mixtures of water and the organic solvents mentioned above can be used. Also, each component may be added separately, or two or more components may be mixed in advance and then mixed with the remaining components,
All components may be mixed at the same time, and the timing of addition or mixing thereof is not particularly limited.

The method of applying the hydrophilic inorganic coating material is not particularly limited, and for example, various usual coating methods such as brush coating, spraying, dipping, roll, flow, curtain, knife coating, spin coating, etc. You can choose the method. The method for curing the coating film of the hydrophilic inorganic paint may be any known method and is not particularly limited. 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 optical semiconductor and the like.

The thickness of the coating-cured film formed from the hydrophilic inorganic coating material is not particularly limited and is, for example, 0.01-1.
The thickness may be about 5 μm, but in order to exhibit various functions of the coating film more effectively, the coating and the cured coating are stably adhered and held for a long period of time, and cracks and peeling do not occur, it is not preferable. 01 to 10 μm is preferable, and 0.01 to
5 μm is more preferable.

The substrate to which the hydrophilic inorganic coating material of the present invention is applied (which is also a substrate used in the hydrophilic coated article of the present invention) is not particularly limited, and examples thereof include an inorganic substrate and an organic substrate. , An inorganic-organic composite substrate, and a coated substrate having at least one layer of an inorganic film and / or at least one layer of an organic film on the surface of any of these.

The inorganic base material is not particularly limited, and examples thereof include a metal base material; a glass base material; a enamel; an inorganic building material such as a water glass decorative board and an inorganic hardened material; The metal base material is not particularly limited, and examples thereof include non-ferrous metals [for example, aluminum (JIS-H4000, etc.), aluminum alloys (duralumin, etc.), copper, zinc, etc.], iron, steel [for example, rolled steel (JIS -G3101 etc.), hot dip galvanized steel (JIS
-G3302), (rolled) stainless steel (JIS-G
4304, G4305, etc.], tin plate (JIS-G3
303 etc.) and other metals in general (including alloys).

The glass substrate is not particularly limited, but examples thereof include sodium glass, Pyrex glass, quartz glass and alkali-free glass. The enamel is a material obtained by baking a glass surface of enamel and coating it on a metal surface. Examples of the base metal include mild steel plate, steel plate, cast iron, and aluminum, but are not particularly limited. The enamel is not particularly limited as long as it is a normal one.

The above-mentioned water glass decorative plate means, for example, a decorative plate obtained by applying sodium silicate to a cement substrate such as slate and baking it. The inorganic hardened body is not particularly limited, but for example, a fiber reinforced cement plate (J
IS-A5430), ceramic siding (JIS-
A5422), wood wool cement board (JIS-A5404)
Etc.), pulp cement board (JIS-A5414 etc.), slate / wood wool cement laminated board (JIS-A5426)
Etc.), gypsum board products (JIS-A6901 etc.), clay roof tiles (JIS-A5208 etc.), thick slate (JIS-
A5402), ceramic tiles (JIS-A5209)
Etc.), concrete blocks for construction (JIS-A540
6 etc.), Terrazo (JIS-A5411 etc.), Prestressed concrete double T slab (JIS-A5412)
Etc.), ALC panel (JIS-A5416 etc.), hollow prestressed concrete panel (JIS-A6511)
Etc.), ordinary bricks (JIS-R1250, etc.) and the like, and all the base materials obtained by curing and molding an inorganic material.

The ceramic substrate is not particularly limited, but examples thereof include alumina, zirconia, silicon carbide, silicon nitride and the like. As an organic base material,
For example, but not limited to, plastic, wood,
Examples include wood and paper. As a plastic substrate,
Although not particularly limited, for example, thermosetting or thermoplastic plastics such as polycarbonate resin, acrylic resin, ABS resin, vinyl chloride resin, epoxy resin, and phenol resin, and these plastics are reinforced with organic fiber such as nylon fiber. Fiber-reinforced plastic (FRP) and the like.

The inorganic-organic composite base material is not particularly limited, but, for example, the above-mentioned plastic may be made of glass fiber,
Fiber reinforced plastics (FRP) reinforced with inorganic fibers such as carbon fibers can be used. The organic coating film constituting the coating substrate is not particularly limited, but for example, acrylic, alkyd, polyester, epoxy, urethane, acrylic silicone, chlorinated rubber, phenolic, melamine, etc. Examples include a cured film of a coating material containing an organic resin.

The inorganic coating film constituting the coating substrate is not particularly limited, but examples thereof include a cured coating film of a coating material containing an inorganic resin such as a silicone resin. When applying the hydrophilic inorganic coating material of the present invention to the base material, depending on the material and surface condition of the base material, it may be difficult to obtain adhesion and weather resistance when the hydrophilic inorganic coating material of the present invention is applied as it is, If necessary, a primer layer may be preliminarily formed on the surface of the base material before forming the coating and cured film of the hydrophilic inorganic coating material of the present invention. The primer layer may be organic or inorganic and is not particularly limited, but examples of the organic primer layer include nylon resin, alkyd resin, epoxy resin, acrylic resin, organic modified silicone resin (for example, acrylic silicone resin, etc.). , Chlorinated rubber resin, urethane resin, phenol resin,
At least one organic resin selected from the group consisting of polyester resin and melamine resin as solid content 1
Examples of the inorganic primer layer include a cured resin layer of an organic primer composition containing 0% by weight or more, and examples of the inorganic primer layer include a cured resin of an inorganic primer composition containing 90% by weight or more of an inorganic resin such as a silicone resin as a solid content. Layers and the like.

The thickness of the primer layer is not particularly limited, but is preferably 0.1 to 50 μm, for example, 0.5.
It is more preferably 10 μm. If this thickness is too thin, adhesion and weather resistance may not be obtained, and if it is too thick, foaming etc. may occur during drying. A base material having at least one organic primer layer and / or inorganic primer layer as described above on its surface is included in the category of the coating base material. That is, the coating film on the surface of the coating substrate may be the primer layer.

Further, the primer layer may contain a coloring agent such as a pigment or dye for toning, if necessary. Examples of usable colorants include those described above as those that can be added to the hydrophilic inorganic coating material. The preferable numerical range of the amount of the colorant compounded in the primer layer is the same as in the case of the hydrophilic inorganic coating material described above. However, it is not based on 100 parts by weight of the total condensation compound-equivalent solid content, but 100% by weight of the total resin solid content in the total amount of the primer composition.
Specified for parts by weight.

The form of the substrate is not particularly limited, and examples thereof include a film form, a sheet form, a plate form, and a fiber form. Further, the base material may be a molded body of a material having these shapes, or a structural body partially including at least one of the materials having these shapes or the molded body thereof. The base material may consist of the above-mentioned various materials alone, a composite material formed by combining at least two of the above-mentioned various materials, or a laminated material formed by stacking at least two of the above-mentioned various materials. But it's okay.

The hydrophilic inorganic coating material and the hydrophilic coated article of the present invention exhibit surface hydrophilicity from the beginning of film formation and can exhibit functions such as antifogging property and antifouling property. Moreover, it is possible to continue the above function due to the hydrophilicity of the surface for a very long period. Therefore, by equipping at least a part of various materials or articles with the coating and curing coating of the hydrophilic inorganic coating material of the present invention, it can be suitably used for the following applications.

Members or articles related to buildings, for example, exterior materials (for example, outer wall materials, flat roof tiles, Japanese roof tiles, roof tiles such as metal roof tiles, etc.), resin rain gutters such as PVC rain gutters, metal such as stainless rain gutters, etc. Rain gutters such as rain making gutters, gates and members used therefor (for example, gates, gateposts, gate fences, etc.), fences (fences) and members used therefor, garage doors,
Home terraces, doors, pillars, carports, bicycle parking ports, sign posts, delivery posts, wiring equipment such as switchboards, switches, gas meters, intercoms, TV doorphones and camera lens parts, electric locks, entrance poles,
Edges, ventilating fan outlets, building glass, etc .; windows (for example, daylighting windows, skylights, louvers, etc. open / close windows, etc.) and members used therefor (for example, window frames, shutters, blinds, etc.), automobiles, railway vehicles, Aircraft, ships, machinery,
Road peripherals (for example, soundproof walls, tunnel interior boards, various display devices, guardrails, car stops, railings, traffic sign boards and signs, traffic lights, post cones, etc.), advertising towers, outdoor or indoor lighting equipment and Members for use (for example, members made of at least one material selected from the group consisting of glass, resin, metal and ceramics), glass for solar cells, vinyl for agriculture and glass houses, outdoor unit for air conditioners , VHF / UH
Antennas for F / BS / CS etc.

The hydrophilic inorganic coating material of the present invention may be directly applied to at least a part of the above-mentioned various materials or articles and cured, but not limited thereto. For example, the hydrophilic inorganic coating material of the present invention may be used. May be applied to the surface of a film substrate and cured to adhere a hydrophilic film to at least a part of the above various materials or articles. Examples of the material for the base material of such a film include polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, vinyl chloride resin, acrylic resin, fluororesin, polypropylene (PP) resin and composite resins thereof. However, the resin is not particularly limited.

[0082]

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples. In Examples and Comparative Examples, all "parts" are "parts by weight" and all "%" are "% 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> Raw material (A ₁ ) of organosiloxane (A)
To 100 parts (0.74 mol) of methyltrimethoxysilane as a nonionic silane-modified surfactant (X12-641 manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane-modified surfactant.
6.1 parts (0.026 mol), tetraethoxysilane 10 as a raw material (A ₂ ) for the organosiloxane (A)
Part (0.048 mol), IPA organosilica sol (trade name "OSCAL1432", manufactured by Catalyst Kasei Kogyo Co., Ltd.), which is also acidic colloidal silica as a raw material (A ₂ ).
90 parts (0.45 mol) of solid content 30%, 30 parts (0.25 mol) of dimethyldimethoxysilane as a raw material (A ₃ ) for the organosiloxane (A), and isopropyl alcohol (IPA in the present specification) as a diluting solvent. (Sometimes abbreviated) 100 parts were mixed, and 90 parts of water was further added and stirred. The obtained liquid is heated in a constant temperature bath of 60 ° C. for 5 hours to adjust the weight average molecular weight (Mw) of the organosiloxane (A) as a reaction product to 1200 to 1800, and to contain a silane-modified surfactant. Thus, an alcohol solution of organosiloxane was obtained. This is called a hydrophilic inorganic paint (1).

Preparation conditions for the hydrophilic inorganic coating material (1): [water] / [OR ¹ ] molar ratio 1.67 ・ Weight average molecular weight of organosiloxane (A) 1200 to 1800 ・ Solid content calculated as total condensation compound 26. 4% Next, the hydrophilic inorganic paint (1) is applied to a glass substrate (50 mm × 50 mm × 2.5 mm) washed with acetone by a spray coating method, and the coating film is dried and cured at a temperature of 150 ° C. for 15 minutes. Thus, a hydrophilic coated product (1) was obtained. The film thickness after curing of the coating film was 0.5 μm. <Example 2> A hydrophilic inorganic coating material (2) was obtained in the same manner as in Example 1 except that the addition amount of the silane-modified surfactant was changed to 323 parts (0.52 mol). .

Next, a hydrophilic coated article (2) was obtained in the same manner as in Example 1 except that the hydrophilic inorganic coating material (2) was used in place of the hydrophilic inorganic coating material (1). It was <Example 3> A hydrophilic inorganic coating material (3) was obtained in the same manner as in Example 1 except that the addition amount of the silane-modified surfactant was changed to 639 parts (1.03 mol). .

Next, a hydrophilic coated article (3) was obtained in the same manner as in Example 1 except that the hydrophilic inorganic coating (3) was used in place of the hydrophilic inorganic coating (1). It was
Next, prior to the following examples, the components (B) and (C) of the silicone resin (2) used therein were prepared as follows. At that time, the silane-modified surfactant was added to the preparation solution of the component (B), and the colloidal silica (D) was dispersed in the preparation solution of the component (B) to be introduced. (Preparation Example of Component B): <Preparation Example B-1> In a flask equipped with a stirrer, a heating jacket, a condenser and a thermometer, IPA-dispersed colloidal silica sol IPA-ST (particle diameter 10 to 20 nm,
Solid content 30%, water content 0.5%, manufactured by Nissan Chemical Industries, Ltd.)
100 parts (0.5 mol), 3.1 parts (0.005 mol) of a nonionic silane-modified surfactant (X12-641 manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane-modified surfactant, and methyltrimethoxy. 68 parts of silane (0.5 mol) and 1 part of water
0.8 parts of the organosilane oligomer (B-1) containing a silane-modified surfactant was obtained by adding 0.8 parts of the mixture, carrying out a partial hydrolysis reaction at 65 ° C. for about 5 hours with stirring, and then cooling. A silica dispersion solution of was obtained. This product had a solid content of 36% in terms of total condensation compound when left to stand at room temperature for 48 hours.

B-1 silica dispersion solution preparation conditions: -mol number of water per mol equivalent of hydrolyzable group of hydrolyzable organosilane 0.4 mol-conversion of all condensation compounds in silica dispersion solution of B-1 Silica content relative to solid content: 45.3% Mol% of hydrolyzable organosilane of m = 1 based on the total amount of hydrolyzable organosilane 100 mol% <Preparation Example B-2> An organosilane oligomer (B-2) containing a silane-modified surfactant in the same manner as in Preparation Example B-1 except that the addition amount of the surfactant was changed to 160 parts (0.25 mol).
A silica dispersion solution of was obtained. This product had a solid content of 60.7% in terms of total condensation compound when left at room temperature for 48 hours.

B-2 silica dispersion solution preparation conditions: -Number of moles of water to 1 mol equivalent of hydrolyzable group of hydrolyzable organosilane 0.27 mol-Conversion of all condensation compounds in silica dispersion solution of B-2 Silica content relative to solid content 14.6% Mol% of hydrolyzable organosilane of m = 1 relative to the whole hydrolyzable organosilane 100 mol% <Preparation Example B-3> In Preparation Example B-1, silane modification A silica dispersion solution of an organosilane oligomer (B-3) containing a silane-modified surfactant in the same manner as in Preparation Example B-1 except that the addition amount of the surfactant was changed to 962 parts (1.5 mol). Got This product had a solid content in terms of total condensation compounds of 80.5% when left at room temperature for 48 hours.

Preparation Conditions for B-3 Silica Dispersion Solution: -Number of moles of water to 1 mol equivalent of hydrolyzable group of hydrolyzable organosilane 0.1 mol-Conversion of all condensation compounds in silica dispersion B-3 Silica content based on solid content 3.7% Mol% of hydrolyzable organosilane of m = 1 relative to the whole hydrolyzable organosilane 100 mol% (preparation example of C component): <Preparation example C-1> Stirrer In a flask equipped with a heating jacket, a condenser, a dropping funnel and a thermometer, a solution of 220 parts (1 mol) of methyltriisopropoxysilane dissolved in 150 parts of toluene was charged.
108 parts of a 1% hydrochloric acid aqueous solution was added dropwise over 20 minutes, and methyltriisopropoxysilane was hydrolyzed at 60 ° C. with stirring. After 40 minutes from the end of the dropping, stirring was stopped, and the reaction solution was transferred to a separating funnel and allowed to stand still, whereby two layers were separated.
The lower layer mixed solution of water and isopropyl alcohol containing a small amount of hydrochloric acid was separated and removed, and the hydrochloric acid remaining in the resin solution of toluene left behind was removed by washing with water. By diluting the product with isopropyl alcohol, a weight average molecular weight (Mw) of about 200 is obtained.
0 silanol group-containing polyorganosiloxane (C-
An isopropyl alcohol solution of 1) was obtained. The solid content in terms of total condensation compound in this solution is 40%. Further, silanol group-containing polyorganosiloxane (C
It has been confirmed that -1) satisfies the average composition formula (II).

(B) and (C) obtained as described above
The following examples were performed using each solution of the components. <Example 4> 40 parts of a silica dispersion solution of B-1 (about 14 parts as a total condensation compound equivalent solid content) and 60 parts of a C-1 isopropyl alcohol solution (24 parts as a total condensation compound equivalent solid content). Hydrophilic inorganic coating material (4)
Got

Next, a hydrophilic coated article (4) was obtained in the same manner as in Example 1 except that the hydrophilic inorganic coating material (4) was used in place of the hydrophilic inorganic coating material (1). It was <Example 5> In Example 4, except that 40 parts of the silica dispersion solution of B-2 was replaced with 40 parts of the silica dispersion solution of B-1 (about 24 parts as the total condensation compound-equivalent solid content). A hydrophilic inorganic coating material (5) was obtained in the same manner as in Example 4.

Next, a hydrophilic coated article (5) was obtained in the same manner as in Example 1 except that the hydrophilic inorganic coating (5) was used in place of the hydrophilic inorganic coating (1). It was <Example 6> In Example 4, 40 parts of the silica dispersion solution of B-3 was used instead of 40 parts of the silica dispersion solution of B-1 (about 32.2 parts as the total condensation compound-equivalent solid content). Hydrophilic inorganic paint (6) in the same manner as in Example 4 except for the above.
Got

Next, a hydrophilic coated article (6) was obtained in the same manner as in Example 1 except that the hydrophilic inorganic coating material (6) was used in place of the hydrophilic inorganic coating material (1). It was <Example 7> Hydrophilic inorganic coating material (1) obtained in Example 1
In addition, titanium oxide sol (titanium oxide sol manufactured by Ishihara Sangyo Co., Ltd .: trade name "STS-01") was used as an optical semiconductor for 100 parts in total of the total condensation compound-equivalent solid content and all optical semiconductor components in the total amount of the coating material. A hydrophilic inorganic coating material (7) was obtained by adding and mixing the photo-semiconductor in an amount of 50 parts.

Next, a hydrophilic coated article (7) was obtained in the same manner as in Example 1 except that the hydrophilic inorganic coating material (7) was used in place of the hydrophilic inorganic coating material (1). It was <Example 8> Hydrophilic inorganic coating material (4) obtained in Example 4
In addition, titanium oxide sol (titanium oxide sol manufactured by Ishihara Sangyo Co., Ltd .: trade name "STS-01") was used as an optical semiconductor for 100 parts in total of the total condensation compound-equivalent solid content and all optical semiconductor components in the total amount of the coating material. A hydrophilic inorganic coating material (8) was obtained by adding and mixing the photo-semiconductor in an amount of 50 parts.

Next, a hydrophilic coated article (8) was obtained in the same manner as in Example 1 except that the hydrophilic inorganic coating material (8) was used in place of the hydrophilic inorganic coating material (1). It was <Example 9> Hydrophilic inorganic coating material (1) obtained in Example 1
In addition, as an antistatic agent, methanol-dispersed antimony oxide-
Zinc oxide (manufactured by Nissan Kagaku Co., Ltd., trade name "SELNAC CX-Z
Hydrophilic inorganic coating material (9) was obtained by adding and mixing 20 parts of 200M ") to 100 parts of the total solids-conversion solid content in the total amount of the coating material.

Next, a hydrophilic coated article (9) was obtained in the same manner as in Example 1 except that the hydrophilic inorganic coating (9) was used in place of the hydrophilic inorganic coating (1). It was <Example 10> Methanol-dispersed antimony oxide-zinc oxide as an antistatic agent was added to the hydrophilic inorganic coating material (4) obtained in Example 4 (manufactured by Nissan Kagaku Co., Ltd. under the trade name "Cernac C").
X-Z200M ”) is added and mixed with 20 parts of 100 parts of the total condensation compound-equivalent solid content in the total amount of the paint.
A hydrophilic inorganic paint (10) was obtained.

Next, a hydrophilic coated article (10) was obtained in the same manner as in Example 1 except that the hydrophilic inorganic coating material (10) was used in place of the hydrophilic inorganic coating material (1). It was <Example 11> In the hydrophilic inorganic coating material (1) obtained in Example 1, a benzotriazole-based ultraviolet absorber (manufactured by CIBA-GEIGY, trade name "TI" was used as an ultraviolet absorber.
NUVIN 384 ") was added and mixed in an amount of 10 parts with respect to 100 parts of the total solid content of the condensed compound in the total amount of the paint, to obtain a hydrophilic inorganic paint (11).

Next, a hydrophilic coated article (11) was obtained in the same manner as in Example 1 except that the hydrophilic inorganic coating material (11) was used in place of the hydrophilic inorganic coating material (1). It was <Example 12> In the hydrophilic inorganic coating material (4) obtained in Example 4, a benzotriazole-based ultraviolet absorber (manufactured by CIBA-GEIGY, trade name "TI" was used as an ultraviolet absorber.
NUVIN 384 ") was added and mixed with 10 parts by weight of the total solid content of 100 parts by weight of the total condensation compound in the total amount of the coating material to obtain a hydrophilic inorganic coating material (12).

Next, a hydrophilic coated article (12) was obtained in the same manner as in Example 1 except that the hydrophilic inorganic coating (12) was used in place of the hydrophilic inorganic coating (1). It was <Example 13> In the hydrophilic inorganic coating material (1) obtained in Example 1, titanium oxide powder (Ishihara Sangyo Co., Ltd., trade name "R-820") was used as a pigment in the total amount of the coating material. 20 parts per 100 parts of condensed compound equivalent solid content,
A hydrophilic inorganic paint (13) was obtained by dispersing for 1 hour with a paint shaker.

Next, a hydrophilic coated article (13) was obtained in the same manner as in Example 1 except that the hydrophilic inorganic coating (13) was used in place of the hydrophilic inorganic coating (1). It was <Example 14> In the hydrophilic inorganic coating material (4) obtained in Example 4, titanium oxide powder (trade name "R-820" manufactured by Ishihara Sangyo Co., Ltd.) was used as a pigment in the total amount of the coating material. 20 parts per 100 parts of condensed compound equivalent solid content,
A hydrophilic inorganic paint (14) was obtained by dispersing for 1 hour with a paint shaker.

Next, a hydrophilic coated article (14) was obtained in the same manner as in Example 1 except that the hydrophilic inorganic coating (14) was used in place of the hydrophilic inorganic coating (1). It was <Comparative Example 1> Stirrer, heating jacket, condenser,
In a flask equipped with a dropping funnel and a thermometer, 100 parts (0.74 mol) of methyltrimethoxysilane as a raw material (A ₁ ) of the organosiloxane (A) and tetra as a raw material (A ₂ ) of the organosiloxane (A). 20 parts (0.096 mol) of ethoxysilane, IPA-dispersed colloidal silica sol IPA-ST (particle size 10 to 20 nm, solid content 30%, water content 0.5%, manufactured by Nissan Chemical Industries, Ltd.) as a raw material (A ₂ ). ) 105 parts (0.53 mol), 30 parts (0.25 mol) of dimethyldimethoxysilane as a raw material (A ₃ ) for the organosiloxane (A), and 100 parts of isopropanol as a diluent solvent were added, and 90 parts of water was added dropwise. After the hydrolysis / polycondensation reaction is carried out at 25 ° C. for 30 minutes while stirring, the weight average molecular weight (M
w) An alcoholic solution of 1000 to 1500 organosiloxane was obtained. This is referred to as a comparative inorganic paint (1).

Preparation conditions of the comparative inorganic coating material (1): [water] / [OR ¹ ] molar ratio 1.36 ・ Weight average molecular weight of organosiloxane (A) 1000 to 1500 ・ Solid content calculated as total condensation compound 23. 3% Next, in Example 1 except that the comparative inorganic paint (1) was used in place of the hydrophilic inorganic paint (1).
Comparative coated product (1) was obtained in the same manner as described above. <Comparative Example 2> Comparative inorganic coating material (1) obtained in Comparative Example 1
In addition, titanium oxide sol (titanium oxide sol manufactured by Ishihara Sangyo Co., Ltd .: trade name "STS-01") was used as an optical semiconductor for 100 parts in total of the total condensation compound-equivalent solid content and all optical semiconductor components in the total amount of the coating material. A comparative inorganic coating material (2) was obtained by adding and mixing 50 parts of the optical semiconductor.

Then, a comparative coated article (2) was obtained in the same manner as in Example 1 except that the comparative inorganic coating (2) was used in place of the hydrophilic inorganic coating (1). It was <Comparative Example 3> Comparative inorganic coating material (1) obtained in Comparative Example 1
In addition, as a general surfactant, a nonionic surfactant (manufactured by Asahi Denka Kogyo Co., Ltd .; trade name "ADEKA REASO NE"
-10 ") is the total solid content of the condensed compound 1 in the total amount of the paint 1
A comparative inorganic coating material (3) was obtained by adding and mixing 0.5 parts with respect to 00 parts.

Then, a comparative coated article (3) was obtained in the same manner as in Example 1 except that the comparative inorganic coating (3) was used in place of the hydrophilic inorganic coating (1). It was <Example 15> Lithium acetate is added to the hydrophilic inorganic coating material (1) obtained in Example 1 as a curing catalyst in an amount of 0.2 with respect to 100 parts by weight of the total condensation compound-equivalent solid content of the hydrophilic inorganic coating material (1). Hydrophilic inorganic coating material (15) was obtained by adding in a ratio of 1 part.

Next, a glass plate washed with acetone (50 m
m × 50 mm × 2.5 mm) surface is spray-coated with an epoxy-based primer (Isam Paint Co., Ltd .: trade name “E-1 primer”) to a film thickness of about 10 μm, and then a hydrophilic inorganic paint (15) Was coated by a spray coating method to a cured film thickness of 0.5 μm, and then dried and cured at room temperature for 1 week to obtain a hydrophilic coated article (15). <Example 16> Hydrophilic coating was carried out in the same manner as in Example 15 except that the hydrophilic inorganic paint (4) obtained in Example 4 was used instead of the hydrophilic inorganic paint (1). The product (16) was obtained. <Example 17> First, the primer composition is used (17
Components -1) to (17-4) were prepared as follows.

Preparation of component (17-1): In a flask equipped with a stirrer, a heating jacket, a condenser and a thermometer, IPA-dispersed colloidal silica sol IPA-ST (particle size 10 to 20 nm, solid content 30%, water content 0). 0.5%, manufactured by Nissan Chemical Industries Ltd., 100 parts, methyltrimethoxysilane 68 parts, and water 2.2 parts were added, and the partial hydrolysis reaction was carried out at 65 ° C. for about 5 hours while stirring. After going
By cooling, a silica dispersion oligomer solution of organosilane was obtained. This is referred to as component (17-1).
This product had a solid content in terms of total condensation compounds of 37.3% when left at room temperature for 48 hours.

(17-1) Component Preparation Conditions: -Mole number of water per mol equivalent of hydrolyzable group 0.1 mol-Silica content of component (17-1) 47.3% -m = 1 Of the hydrolyzable organosilane of 100 mol% (17-2) Component: of the silanol group-containing polyorganosiloxane (C-1) having a weight average molecular weight (Mw) of about 2000 obtained in Preparation Example C-1 A 40% isopropyl alcohol solution is referred to as component (17-2).

Component (17-3): As the component (17-3), N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane is referred to as E-1, and dibutyltin dilaurate is referred to as E-2. (17-4) Preparation of component: Next, in a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel, a nitrogen gas inlet / outlet port, and a thermometer, 5.69 parts of n-butyl methacrylate (BMA). (40 mmol), trimethoxysilylpropyl methacrylate (SMA)
1.24 parts (5 mmol), glycidyl methacrylate (GMA) 0.71 part (5 mmol), and γ-mercaptopropyltrimethoxysilane as a chain transfer agent.
Azobisisobutyronitrile (0.04 parts) was added to a reaction solution prepared by dissolving 784 parts (4 mmol) in 8.49 parts of toluene.
A solution obtained by dissolving 25 parts (0.15 mmol) in 3 parts of toluene was added dropwise under a nitrogen stream and reacted at 70 ° C. for 2 hours. As a result, a 40% toluene solution of an acrylic resin having a weight average molecular weight Mw of 1000 was obtained. This is (17
-4) It is called a component.

(17-4) Component Preparation Conditions: Monomer molar ratio BMA / SMA / GMA = 8/1/1 Weight average molecular weight 1000 Solid content 40% And mix with isopropyl alcohol to give a solid content of 25
The primer composition was obtained by diluting so as to be%. Acrylic plate (50mm
X 50 mm x 2.5 mm) was applied by a spray coating method to a cured coating film thickness of 1.0 µm and cured at 60 ° C for 15 minutes to form a primer layer.

After forming the primer layer, set for 10 minutes.
The hydrophilic inorganic coating material obtained in Example 15 (1
5) is applied by spray coating to obtain a cured coating film thickness of 0.5 μm
And then dry and cure at room temperature for 1 week
Thus, a hydrophilic coated product (17) was obtained. <Example 18> The hydrophilic inorganic coating composition of Example 17
Hydrophilic inorganic coating obtained in Example 4 instead of (1)
Hydrophilic in the same manner as in Example 17 except that (4) was used.
A coated product (18) was obtained. <Example 19> Toyota Sprinter- (Automobile; 1990)
After thoroughly washing the bonnet of the formula) with acetone,
The hydrophilic inorganic paint (4) obtained in No. 4 was spray coated.
Apply so that the thickness of the cured coating is 0.5 μm, and apply at room temperature.
Hydrophilic coated products by drying and curing day and night (19)
Got <Example 20> General Technical Research Institute (Building; Matsushita Electric Works, Ltd.)
Part of the eastern surface of Kadoma City, Osaka Prefecture (10m²) Washed with dilute hydrochloric acid
After that, the hydrophilic inorganic paint (4) obtained in Example 4 is applied on the base.
With a brush to apply a cured film thickness of 1.0 μm
By drying and curing at a temperature of about 20 ° C all day and night,
An aqueous coated product (20) was obtained. <Example 21> Matsushita Electric Works Ltd. Osaka Kadoma Research Center
Matsushita Electric Works Co., Ltd. daylighting window (Model M installed on the roof of the building
WT2025JH) to a part of the hydrophilicity obtained in Example 1.
Of inorganic inorganic coating (1) by dipping method
It is applied so that it becomes μm, and dried and cured at 150 ° C for 30 minutes.
By doing so, a hydrophilic coated product (21) was obtained. Example 22 Matsushita Electric Works, Ltd. Osaka Kadoma One-way street
Part of the road sign (about 1500 cm) ²) In Example 4
Harden the hydrophilic inorganic paint (4) obtained in
Apply the chemical coating to a thickness of 0.5 μm and leave it at room temperature for one day.
By drying and curing at night, hydrophilic coated product (22)
Obtained. <Example 23> Matsushita Electric Works, Ltd. Osaka Kadoma One-sided street
Part of a row of building display signs (about 500 cm²), The example
The hydrophilic inorganic paint (4) obtained in No. 4 was spray coated.
Apply so that the thickness of the cured coating is 0.5 μm, and apply at room temperature.
Hydrophilic coated products by drying and curing day and night (23)
Got Example 24 Matsushita Electric Works, Ltd. Osaka Building
Window glass (1m², Thickness of 6 mm)
The hydrophilic inorganic paint (4) obtained in 4 was applied by the flow coating method.
Apply the coating so that the thickness of the cured coating is 0.1 μm.
Hydrophilic coated products by drying and curing day and night (24)
Got <Example 25> Matsushita Electric Works, Ltd. Osaka Main gate at the main gate
The entire surface of the installed road lighting equipment (model YA32020)
The hydrophilicity obtained in Example 4 was applied to a part of the lath, the pole, and the device.
Of inorganic inorganic paint (4) by spray coating
It is applied so that it becomes μm, and it is dried and cured at room temperature for 24 hours.
By doing so, a hydrophilic accessory (25) was obtained. <Example 26> Matsushita Electric Works, Ltd. Osaka Kadoma in-house food
Fuji-type fluorescent lamp fixtures (model FA22 installed in the kitchen of the hall)
063) to a part of the reflective plate, the hydrophilicity obtained in Example 1
Inorganic paint (1) cured by spray coating method Coating thickness 0.5μ
m, and dried and cured at 100 ° C for 20 minutes.
By doing so, a hydrophilic coated product (26) was obtained. <Example 27> In Example 1, the silane-modified surface activity was used.
Olga was prepared in the same manner as in Example 1 except that no agent was added.
An alcohol solution of nosiloxane (A) was obtained.

Preparation conditions of alcohol solution of organosiloxane (A): [water] / [OR ¹ ] molar ratio 1.67 ・ weight average molecular weight 1500 ・ solid content of total condensation compound 26.4% Silane was added to this solution. As a modified surfactant, a nonionic silane modified surfactant (X12-64 manufactured by Shin-Etsu Chemical Co., Ltd.)
A hydrophilic inorganic coating material (27) was obtained by adding and mixing 639 parts (1.03 mol) of 1).

Next, a hydrophilic coated article (27) was obtained in the same manner as in Example 1 except that the hydrophilic inorganic coating (27) was used in place of the hydrophilic inorganic coating (1). It was <Example 28> An organosilane oligomer (B-4) containing no silane-modified surfactant was prepared in the same manner as in Preparation Example B-1 except that no silane-modified surfactant was used. A silica dispersion solution was obtained. This product had a solid content of 36% in terms of total condensation compound when left to stand at room temperature for 48 hours.

Preparation Conditions for B-4 Silica Dispersion Solution: -Number of moles of water to 1 mol equivalent of hydrolyzable group of hydrolyzable organosilane 0.4 mol-Conversion of all condensed compounds in silica dispersion solution of B-4 Silica content relative to solid content: 16.5% Mol% of hydrolyzable organosilane of m = 1 based on total of hydrolyzable organosilane 100 mol% Next, in Example 4, silica dispersion solution B-1 40
40 parts of the silica dispersion solution of the organosilane oligomer (B-4) obtained above (about 14 parts as the total condensation compound-equivalent solid content) is used in place of the parts, and this solution is mixed with isopropyl alcohol of C-1. As a silane-modified surfactant when mixed with a solution and a curing catalyst, a nonionic silane-modified surfactant (X12-6 manufactured by Shin-Etsu Chemical Co., Ltd.)
A hydrophilic inorganic coating material (28) was obtained in the same manner as in Example 4 except that 962 parts (1.5 mol) of 41) were added and mixed.

Next, a hydrophilic coated article (28) was obtained in the same manner as in Example 1 except that the hydrophilic inorganic coating (28) was used in place of the hydrophilic inorganic coating (1). It was <Example 29> In Preparation Example B-1, no colloidal silica was used, and 0.001 was used instead of water.
A solution of silica-free organosilane oligomer (B-5) was obtained in the same manner as in Preparation Example B-1 except that 12 parts of N-HCl was added. This product had a solid content of 44% in terms of total condensation compound when left to stand at room temperature for 48 hours.

Next, in Example 4, instead of 40 parts of the silica dispersion solution of B-1, 40 parts of the solution of the organosilane oligomer (B-5) obtained above (as a total condensation compound-equivalent solid content was 17 parts). .6 parts), and when this solution is mixed with an isopropyl alcohol solution of C-1 and a curing catalyst, IPA-dispersed colloidal silica sol IPA-ST (particle diameter 10 to 20 nm, solid content 30%,
A hydrophilic inorganic coating material (29) was obtained in the same manner as in Example 4 except that 0.5% of water and 100 parts of Nissan Chemical Industries, Ltd. were added.

Next, a hydrophilic coated article (29) was obtained in the same manner as in Example 1 except that the hydrophilic inorganic coating (29) was used in place of the hydrophilic inorganic coating (1). It was The coating film properties of the paints and coated products obtained as described above were evaluated by the following methods. <Evaluation Method> Adhesion: Adhesion to the substrate is evaluated by a cross-cut adhesive tape (using cellophane tape) peeling test.

Coating film hardness: Pencil hardness test (JIS-K54
According to 00). Hydrophilicity (wettability to water): The contact angle between water and the cured coating is 24 hours immediately after the cured coating is prepared (initial contact angle) and the ultraviolet irradiation device (Oak Seisakusho "Handy UV300") is applied to the cured coating for 24 hours. It evaluated by measuring after irradiation (contact angle after UV irradiation). Contact angle is 0.2c
Distilled water of c was dropped on the surface of the cured film and then observed with a magnifying camera. The smaller the contact angle, the higher the hydrophilicity.

Evaluation of articles and the like coated: Evaluation was made by the difference in how the coated and unpainted areas were stained 3 months after coating. The results are shown in Tables 1 to 3.

[0118]

[Table 1]

[0119]

[Table 2]

[0120]

[Table 3]

From Tables 1 to 3, the following was confirmed. That is, since the coating films formed in the examples all contain a silane-modified surfactant, the contact angle is several degrees from the initial stage after film formation and the hydrophilicity is high, and the hydrophilicity is high even after irradiation with ultraviolet rays. Holds and has high hydrophilic durability. On the other hand, the coating film of Comparative Example 1 containing no silane-modified surfactant has a large contact angle both at the initial stage after film formation and after irradiation with ultraviolet rays, and has low hydrophilicity. The coating film of Comparative Example 2 containing no silane-modified surfactant but containing a photo-semiconductor had a large contact angle and low hydrophilicity in the initial stage after film formation, and the contact angle became small and high hydrophilicity only after irradiation with ultraviolet rays. Sex has been obtained. The coating film of Comparative Example 3 in which a general surfactant was used instead of the silane-modified surfactant had a small contact angle and high hydrophilicity in the early stage after film formation, but had a large contact angle after ultraviolet irradiation. Hydrophilicity is reduced and hydrophilicity is not durable.

Incidentally, Examples 19 to 2 in which the article was coated
With respect to No. 6, in all cases, the adhesion of dirt in the coated part was hardly seen as compared with the unpainted part.

[0123]

EFFECT OF THE INVENTION The hydrophilic inorganic coating material of the present invention contains a surfactant, and since the surfactant has an effect of imparting hydrophilicity, it exhibits surface hydrophilicity from the beginning of film formation and prevents It is possible to form a coating film that exhibits functions such as cloudiness and antifouling properties. Further, since the silane-modified surfactant is used as the surfactant, the formed coating film has a hydrophilic group of the surfactant bonded to the main skeleton of the coating film, and The surfactant hardly deteriorates or flows off from the surface of the coating film with the lapse of time, and the above function due to the surface hydrophilicity can be continued for a very long period. Further, it also has an effect of reducing the adhesion of dirt to the coating film.

Since the hydrophilic inorganic coating material of the present invention can form a coating film exhibiting the above-mentioned functions due to the hydrophilicity of the surface without containing an optical semiconductor, it can be used even in a portion which is not exposed to ultraviolet rays. . Furthermore, since the coating material of the present invention is an inorganic coating material, the coating film performance is less likely to be impaired by the addition of various additives such as optical semiconductors, is less likely to be deteriorated by ultraviolet rays, and has weather resistance and durability. An excellent coating-cured film can be formed. Further, it is possible to match various colors.

Since the hydrophilic inorganic coating material of the present invention can be cured not only by heating but also at room temperature, it can be used in a wide range of dry curing conditions or temperature range. Therefore, not only can it be applied to a substrate having a shape that makes it difficult to evenly apply heat, a substrate having a large size, or a substrate having poor heat resistance, but it can also be used when painting outdoors. As it can be painted even when it is difficult to apply heat, its industrial value is high.

Since the hydrophilic coated article of the present invention has the coating and coating film of the above-mentioned hydrophilic inorganic coating on the surface of the substrate, it exhibits surface hydrophilicity from the beginning of film formation, and the resulting anti-fogging It can exhibit functions such as anti-fouling property and antifouling property. Moreover, it is possible to continue the above function due to the hydrophilicity of the surface for a very long period. The hydrophilic coated article of the present invention can exhibit the above function due to the hydrophilicity of the surface without containing a photo-semiconductor in the coating film, and thus can be used even in a place not exposed to ultraviolet rays.

In the hydrophilic coated article of the present invention, since the coating used for forming the coating and cured coating on the surface thereof is an inorganic type, the coating performance may be impaired by the addition of various additives such as optical semiconductors. Less, less likely to deteriorate by ultraviolet rays, and also excellent in weather resistance and durability. Further, since it can be produced using the hydrophilic inorganic coating material that can be adjusted to various colors, it has a high designability and a wide range of use.

Since the hydrophilic coated article of the present invention can be produced by using the above hydrophilic inorganic coating which can be cured not only by heating but also at room temperature, it can be produced within a wide range of dry curing conditions or temperature. Therefore, it is possible to use a base material having a shape that makes it difficult to evenly apply heat, a base material having a large size, or a base material having poor heat resistance, and to be able to manufacture even at work sites where it is difficult to apply heat, such as outdoors. Therefore, its industrial value is high.

The hydrophilic coated article of the present invention is a composite of the hydrophilic inorganic coating material used in its production and various functional materials to control its functional performance, coating film characteristics, etc. according to the intended use. be able to.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C09D 183/04 C09D 183/04 (56) References JP-A-8-141503 (JP, A) JP-A-9-24335 (JP , A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C09D 7 / 12,183 / 04 B05D 5 / 00,7 / 14,7 / 24

Claims (13)

(57) [Claims] To 1. A mineral paint mainly comprising silicone resin, silicone Ri Na contain silane-modified surfactant having a reactive group at its terminal, the silicone resin, comprising the following component (A)
The silane-modified surfactant is represented by the following general formula (a).
Hydrophilic inorganic paint, which is a compound . Component (A): Silicon compound represented by the general formula R ² Si (OR ¹ ) ₃
To the silicon compound represented by the general formula Si (OR ¹ ) ₄
And / or colloidal silica 0.1 to 20 mol
And a silicon compound represented by the general formula R ² ₂ Si (OR ¹ ) ₂
A hydrolyzable mixture containing 0 to 0.6 mol (wherein
R ¹ and R ² are monovalent hydrocarbon groups)
And the weight average molecular weight of the hydrolyzed polycondensate is
Adjusted to be over 900 in terms of polystyrene
Organosiloxane . (A) Compound: General formula R ⁰ _n SiX _4-n (a) (In the formula, R ⁰ is —COOH, —OSO ₃ ^— , —SO ₃ ═N =
⁺ , -OH, the same selected from polyoxyethylene chains
Or a different hydrophilic group, where n is an integer of 1 to 3 and X is
A water-decomposable group is shown. ) 2. A method silicone resin in the inorganic coating composition containing as a main component, Ri Na contain silane-modified surfactant having a reactive group at its terminal, the silicone resin, the following (B), (C), (D)
And hydrolysis of the raw material of the component (B) containing the component (E)
Of at least 50 mol% of the functional organosilanes with m = 1
It is a silicone resin that is a luganosilane, and the silane-modified surfactant is represented by the following general formula (a).
Hydrophilic inorganic paint, which is a compound . Component (B): represented by the general formula R ³ _m SiX _4-m (I) (wherein R ³ may be the same or different substituents
Is an unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and m is
An integer of 0 to 3 and X represents a hydrolyzable group)
Luganosilane is used as an organic solvent, water or a mixed solvent thereof.
In the above, water per unit of 1 equivalent of the hydrolyzable group (X) is 0.
Partially hydrolyzed under the condition of using 001 to 0.5 mol
An organosilane oligomer composed of Component (C): represented by the average composition formula R ⁴ _a Si (OH) _b O _{(4-ab) / 2} (II) (wherein R ⁴ is the same or different substitution or
An unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms,
And b are 0.2 ≦ a ≦ 2 and 0.0001 ≦ b ≦, respectively.
3, a number that satisfies the relationship of a + b <4),
A polyorganosiloxane containing a ranol group. Component (D): silica. Component (E): curing catalyst. (A) Compound: General formula R ⁰ _n SiX _4-n (a) (In the formula, R ⁰ is —COOH, —OSO ₃ ^— , —SO ₃ ═N =
⁺ , -OH, the same selected from polyoxyethylene chains
Or a different hydrophilic group, where n is an integer of 1 to 3 and X is
A water-decomposable group is shown. ) 3. The silane-modified surfactant is the above (A).
0.02 per 1 mol of all silicon compounds (excluding colloidal silica) which are raw materials of the component (A) at the time of preparing the components
The hydrophilic inorganic coating material according to claim 1 , wherein the hydrophilic inorganic coating material is contained in the coating material by adding it in an amount of 5 to 1 mol. 4. The component (B) comprises the colloidal silica prepared by dispersing the component (D) in an organic solvent, water or a mixed solvent thereof, in which the hydrolyzable organosilane is added to the hydrolyzable group. (X) 0.001 to 1 mol equivalent of water
Partially hydrolyzed under the condition of using 0.5 mol,
The hydrophilic inorganic coating material according to claim 2 , which is a silica-dispersed organosilane oligomer containing 3 to 95% by weight of the component (D) with respect to the total solid content of the component (B) and the component (D). . 5. The silane-modified surfactant is the above (B).
It is contained in the coating composition by adding an amount of 0.01 to 3 mol per 1 mol of total hydrolyzable organosilane which is a raw material of the component (B) at the time of preparing the components. The hydrophilic inorganic coating material according to claim 2 or 4 . 6. A also contains an optical semiconductor, hydrophilic inorganic paint according to any one of claims 1 to 5. Also contain 7. The antistatic agent, claims 1 to 6
The hydrophilic inorganic coating material as described in any of 1. 8. The method according to claim 1, further comprising an ultraviolet absorber.
7. The hydrophilic inorganic coating material according to any one of 7 to 7 . 9. also contains a coloring agent, a hydrophilic inorganic coating according to any one of claims 1 to 8. 10. A hydrophilic coated article having a coating layer formed on the surface of a substrate, the coating layer comprising the hydrophilic inorganic coating composition according to any one of claims 1 to 9 . 11. The base material is an inorganic base material, an organic base material,
An inorganic-organic composite substrate, each single material of a coated substrate having at least one layer of inorganic coating and / or at least one layer of organic coating on the surface of any of these substrates,
The hydrophilic coating according to claim 10 , which is selected from the group consisting of a composite material obtained by combining at least two of these and a laminated material obtained by laminating at least two of these. Goods. 12. The base material is metal, glass, hollow,
Ceramics, cement, concrete, wood, wood, plastics, inorganic fiber reinforced plastics, and a coating base having at least one inorganic coating and / or at least one organic coating on the surface of any of these substrates. 12. The material according to claim 11 , which is selected from the group consisting of each single material of the material, a composite material formed by combining at least two of these materials, and a laminated material formed by stacking at least two of these materials. Hydrophilic coating products. Wherein said said coating coated substrate has a surface is a primer layer, a hydrophilic coated product of claim 11 or 12.