JPH10296185A - Low temperature curing inorganic coating method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable coating using an inorg. coating material which substantially prevents the adhesion of a stains to a coating film even during curing at ordinary temp. by preparing the inorg. coating material of a coating material which consists essentially of a silicone resin and contains a specific ratio of a curing accelerator and curing the coating film at a specific temp. When a coated article by using the inorg. coating material. SOLUTION: The required inorg. coating is executed by using the coating material which consists essentially of the silicone resin and contains the curing accelerator at 2 to 80 pts.wt. per 100 pts.wt. total of the solid content in terms of the condensed compd. of the coating material and the curing accelerator and curing the coating film at a low temp. 100 deg.C. At this time, the silicone resin preferably contains a component (A). The component (A) is the hydrolyzed polycondensdate (R<1> , R<2> are monovalent hydrocarbon groups) contg. 5 to 30000 pts.wt. silicon compd. or colloidal silica expressed by formula the formula Si(OR<1> )4 and 0 to 60 pts.wt. silicon compd. expressed by the formula R<2> XSi(OR<1> )2 per 100 pts.wt. silicon compd. expressed by the formula R<2> Si(OR<1> )3 .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a coating method which uses a novel inorganic coating which is excellent in curability at low temperatures such as normal temperature.

[0002]

2. Description of the Related Art Paints include inorganic paints and organic paints.
The inorganic paint had high weather resistance, but did not cure unless baked. In contrast, organic paints can be cured at low temperatures in most cases. Therefore, in most cases, organic paints are used as paints used for on-site construction. However, organic paints have problems such as low weather resistance and easy staining as compared with inorganic paints.

[0003] Accordingly, an inorganic coating which cures at a low temperature has been developed (see Japanese Patent Application Laid-Open No. 4-175388).

[0004]

However, the above-mentioned low-temperature-curable inorganic coating material is liable to be stained or damaged during the curing. Accordingly, an object of the present invention is to provide a low-temperature curing inorganic coating method that uses an inorganic coating that does not easily adhere to the coating film even during curing at room temperature and does not easily damage the coating film.

[0005]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have repeated various studies and experiments on measures for preventing contamination and damage during curing of the paint.
In the process, a silicone resin is selected as the main component of the inorganic paint, and when a curing accelerator is added to the resin, the curing is accelerated, and the resin cures in a short time even at room temperature, thereby making it difficult for dirt to adhere and to be hardly damaged. The present invention has been completed.

Accordingly, in the low-temperature curing inorganic coating method according to the present invention, when a coated article is obtained by using an inorganic coating as a base material, the inorganic coating mainly comprises a silicone resin;
The curing accelerator contains 2 to 80 parts by weight based on 100 parts by weight of the total of the solid content in terms of the condensation compound of the paint and the curing accelerator, and is characterized in that the coating film is cured at a low temperature of 100 ° C. or less. I do.

The silicone resin is preferably the following silicone resin (1) or (2). The silicone resin (1) contains the following component (A). Component (A): (A ₁ ) 100 parts by weight of a silicon compound represented by R ² Si (OR ¹ ) ₃ with respect to 100 parts by weight of a silicon compound represented by (A ₂ ) Si (OR ¹ ) ₄ And / or 5 to 30,000 parts by weight of colloidal silica,
(A ₃₎ the general formula R ² ₂ Si (OR ¹⁾ a hydrolyzable mixture containing silicon compounds 0 to 60 parts by weight, represented by ₂ (wherein R ^1, R ² represents a monovalent hydrocarbon group ) Wherein the weight-average molecular weight of the hydrolyzed polycondensate is adjusted to 900 or more in terms of polystyrene (hereinafter referred to as "organosiloxane solution (A ) ")).

[0008] The silicone resin (2) comprises the following (B):
Component (C) and (D), wherein component (B) contains 5-95% by weight of silica as a solid content, and
At least 50 mol% of the hydrolyzable organosilane of the component (B) is m = 1 organosilane. Component (B): represented by the general formula R ³ _m SiX _4-m (I) (where 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 represents a hydrolyzable group.) In a colloidal silica dispersed in an organic solvent, water or a mixed solvent thereof, the hydrolyzable group ( X) An organosilane silica-dispersed oligomer solution (hereinafter referred to as “silica-dispersed oligomer solution (B)”) obtained by partially hydrolyzing under the condition of using 0.001 to 0.5 mol of water per mol equivalent. May be called). Component (C): represented by the average composition formula R ⁴ _a Si (OH) _b O _{(4-ab) / 2} ... (II) (where R ⁴ is the same or different and substituted or unsubstituted and has 1 to 1 carbon atoms) 8 represents a monovalent hydrocarbon group, wherein a and b are respectively 0.2 ≦ a ≦ 2, 0.0001 ≦ b ≦
3, a number satisfying the relationship of a + b <4. ), A solution of a polyorganosiloxane containing a silanol group in the molecule (hereinafter referred to as “polyorganosiloxane solution (C)”).
). Component (D): a curing catalyst (hereinafter sometimes referred to as “curing catalyst (D)”).

The curing accelerator, which is one component of the inorganic coating used in the present invention, includes, for example, titanium oxide, zinc oxide, tin oxide,
Iron oxide, zirconium oxide, tungsten oxide, chromium oxide, molybdenum oxide, ruthenium oxide, germanium oxide, lead oxide, cadmium oxide, copper oxide, vanadium oxide, niobium oxide, tantalum oxide, manganese oxide, cobalt oxide, rhodium oxide, nickel oxide And an optical semiconductor comprising at least one metal oxide selected from the group consisting of rhenium oxide.

The curing accelerator may be in the form of a powder or a sol. If the curing accelerator is a sol having a pH of 7 or less, curing can proceed in a shorter time,
Excellent convenience in use. It is preferable that a metal is supported on the surface of the curing accelerator. The metal supported is silver, copper, iron, nickel, zinc, platinum, gold,
It is preferably at least one selected from the group consisting of palladium, cadmium, cobalt, rhodium and ruthenium.

The thickness of the coating film for coating is not particularly limited, but is selected to be approximately 0.01 to 10 μm. 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 inorganic coating film and / or at least one organic coating film on any one of these base materials. Preferably, the material is selected from the group consisting of individual materials of the material, a composite material obtained by combining at least two of these materials, and a laminated material obtained by laminating at least two of these materials.

[0012] The base material may be at least one of metal, glass, hollow, ceramics, cement, concrete, wood, wood, plastic, inorganic fiber reinforced plastic, and any one of these base materials. Single material of a coating substrate having at least one inorganic coating and / or at least one organic coating, a composite material obtained by combining at least two of these, and a laminate of at least two of these materials More preferably, it is selected from the group consisting of laminated materials.

[0013] The coating on the surface of the coating substrate may be a primer layer. The low-temperature curing inorganic coating method according to the present invention is not particularly limited, but is preferably used when obtaining the following coated product. Building-related members (eg, glass, etc.), building gates and members for use therewith (eg, gate posts, etc.), building fences, members for use therewith, windows (eg, daylighting windows, etc.) and members for use therewith (Eg, window frames, etc.), automobiles, machinery, road peripherals (particularly traffic signs), advertising towers, outdoor or indoor lighting fixtures and members for use therewith (eg, glass, resin, metal and ceramics) Or a member made of at least one material selected from the group consisting of:

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The inorganic coating used in the present invention contains a silicone resin as a main component. This silicone resin is used as a film forming component. As silicone resin,
The silicone resin (1) containing the component (A) is preferable in that it does not deteriorate with time even when a curing accelerator is added, and the silicone resin (B) further improves room temperature (normal temperature) curability. ), (C) and (D), more preferably a silicone resin (2).

As a raw material for the component (A) contained in the silicone resin (1), ie, the organosiloxane in the organosiloxane solution (A), a hydrolyzable mixture containing the silicon compounds (A ₁ ) to (A ₃ ) Is used. Silicon compounds other than colloidal silica (A ₁ )
(A ₃₎ of the general formula ^{_{R 2 p Si (OR 1)}} 4-p ... can be grossly represented by (III) (wherein R ^1, R ² represents a monovalent hydrocarbon group, p Is an integer of 0 to 2).

R ² is not particularly limited, and includes, for example, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. Specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl,
Alkyl groups such as heptyl group and octyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aralkyl groups such as 2-phenylethyl group, 2-phenylpropyl group and 3-phenylpropyl group; phenyl group and tolyl group Aryl group; alkenyl group such as vinyl group and allyl group; chloromethyl group, γ-chloropropyl group, 3,3,
Halogen-substituted hydrocarbon groups such as 3-trifluoropropyl group; substituted hydrocarbon groups such as γ-methacryloxypropyl group, γ-glycidoxypropyl group, 3,4-epoxycyclohexylethyl group, γ-mercaptopropyl group, etc. Can be exemplified. 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.

Although there is no particular limitation on R ¹ , for example, those using an alkyl group having 1 to 4 carbon atoms as a main raw material are used. Particularly, tetramethoxysilane, tetraethoxysilane and the like can be exemplified as the tetraalkoxysilane with p = 0, and as the organotrialkoxysilane with p = 1, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane can be exemplified. Phenyltrimethoxysilane, phenyltriethoxysilane, and 3,3,3-trifluoropropyltrimethoxysilane. Examples of the diorganodialkoxysilane having p = 2 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 solution (A) is prepared by, for example, diluting the hydrolyzable mixture with a suitable solvent, adding water as a curing agent thereto and, if necessary, a catalyst (for example, hydrochloric acid, acetic acid, halogenated silane, chloroacetic acid, One or more of organic acids and inorganic acids such as citric acid, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, toluenesulfonic acid, and oxalic acid), etc. Is added in a required amount (heated if necessary (for example, 40 to 10).
0 ° C.) may be prepared by performing hydrolysis and polycondensation 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 so as to be 00 or more, preferably 1000 or more. Molecular weight distribution of prepolymer (weight average molecular weight (M
When w)) is smaller than 900, the curing shrinkage during the condensation polymerization of the silicone resin (1) is large, and cracks are easily generated in the coating film after curing.

Preparation of an organosiloxane solution (A)
Raw materials (A₁) ~ (A_Three) Used amount is (A₁) 10
(A)_Two) 5-30,000 parts by weight (good)
Preferably 10 to 25,000 parts by weight, more preferably 20
20,000 parts by weight), (A _Three) 60 parts by weight or less (preferred)
40 parts by weight or less, more preferably 30 parts by weight or less
Below). (A_Two) Is less than the above range
Not available or (A _Three) Is more than the above range
And the desired hardness of the cured film cannot be obtained.
Problem). Also, (A_TwoAbove)
If it is more than the range, the crosslink density of the cured film is too high and the hardness is too high.
It's too high, so it's easy to crack
There's a problem.

As the raw material (A ₂ ), the general formula Si
One or both of a silicon compound represented by (OR ¹ ) ₄ and colloidal silica are used.
The colloidal silica that can be used is not particularly limited, but, for example, water-dispersible or non-aqueous organic solvent-dispersible 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. The water-dispersible colloidal silica is usually made of water glass, but can be easily obtained as a commercial product. The organic solvent-dispersible colloidal silica can be easily prepared by replacing 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 similarly to the water-dispersible colloidal silica. In the organic solvent dispersible colloidal silica, the type of the organic solvent in which the colloidal silica is dispersed is, for example, methanol, ethanol, isopropanol, n-butanol,
Lower aliphatic alcohols such as isobutanol; ethylene glycol, ethylene glycol monobutyl ether,
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. Can be used. Toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime and the like can also be used in combination with these hydrophilic organic solvents.

When colloidal silica is used as at least a part of the raw material (A ₂ ), the amount of the colloidal silica contained in the above-mentioned amount of (A ₂ ) is a part by weight as a silica component. In addition, water is used as a curing agent used in the hydrolysis polycondensation reaction of the hydrolyzable mixture, and the amount of the water is 1 mole equivalent of OR ¹ group contained in the hydrolyzable mixture. Water 0.01-3.0
Mol is preferable, and 0.3 to 1.5 mol is more preferable.

As the diluting solvent used in the hydrolysis polycondensation reaction of the hydrolyzable mixture, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol and the like described above as a dispersion solvent for colloidal silica are used. And the like; ethylene glycol derivatives such as ethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether acetate; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and diacetone alcohol. One or more of them 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 and the like can also be mentioned.

Further, p of the organosiloxane solution (A)
It is preferable that H is adjusted in the range of 3.8 to 6. When the pH is within this range, the organosiloxane solution (A) can be used stably within the above-mentioned range of molecular weight. If the pH is out of this range, the stability of the organosiloxane solution (A) is poor, so that the usable period from the preparation of the coating is limited. Here, the pH adjustment method is not particularly limited, but, for example,
When the pH of the organosiloxane solution (A) becomes less than 3.8 when the raw materials are mixed, for example, the pH may be adjusted within the above range using a basic reagent such as ammonia. In this case, for example, it may be adjusted using an acidic reagent such as hydrochloric acid. Also, depending on the pH,
If the reaction does not proceed in reverse with low molecular weight and it takes time to reach the molecular weight range, the reaction may be promoted by heating the organosiloxane solution (A), or the pH may be lowered with an acidic reagent. After the reaction is carried out, the pH may be returned to a predetermined value with a basic reagent.

In the present invention, since a curing accelerator is used, the silicone resin (1) does not necessarily need to contain a curing catalyst not only at the time of heat curing but also at the time of room temperature curing. By further accelerating the condensation reaction, a curing catalyst can be further included, if necessary, for the purpose of accelerating the curing of the coating film. Examples of the curing catalyst include, but are not particularly limited to, alkyl titanates; carboxylic acid metal salts such as tin octylate, dibutyltin dilaurate, and dioctyltin dimaleate; dibutylamine-2-hexoate, dimethylamine acetate, and ethanolamine acetate. Amine salts such as tetramethylammonium acetate; amines such as tetraethylpentamine;
Amine-based silane coupling agents such as -β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane; acids such as p-toluenesulfonic acid, phthalic acid and hydrochloric acid Aluminum compounds such as aluminum alkoxides and aluminum chelates; lithium acetate, potassium acetate, lithium formate, sodium formate, potassium phosphate;
Alkali metal salts such as potassium hydroxide; titanium compounds such as tetraisopropyl titanate, tetrabutyl titanate, and titanium tetraacetylacetonate; and halogenated silanes such as methyltrichlorosilane, dimethyldichlorosilane, and trimethylmonochlorosilane. However, other than these, there is no particular limitation as long as it is effective for accelerating 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, more preferably 8% or less, based on the total solid content of the organosiloxane solution (A) in terms of the total condensed compound. is there. If it exceeds 10% by weight, the storage stability of the inorganic paint may be impaired. When the silicone resin contained in the inorganic paint is the silicone resin (1), the inorganic paint is heated at a low temperature or left at room temperature by using the curing accelerating action of a curing accelerator to obtain the component (A). The hydrolyzable groups of the organosiloxane contained therein undergo a condensation reaction to form a cured film. Therefore, such an antistatic inorganic coating is hardly affected by humidity even when it is cured at room temperature. Further, by performing the heat treatment, a condensation film can be further promoted to form a cured film.

The component (B) contained in the silicone resin (2), that is, a silica-dispersed oligomer solution (B)
Is a main component of a base polymer having a hydrolyzable group (X) as a functional group that participates in a curing reaction when forming a cured film of an inorganic paint. For example, one or two types of the hydrolyzable organosilane represented by the general formula (I) may be added to colloidal silica dispersed in an organic solvent or water (a mixed solvent of an organic solvent and water may be used). In addition to the above conditions, water (water previously contained in colloidal silica and / or water added separately) is used in an amount of 0.001 to 0.5 mol of water per 1 mol equivalent of the hydrolyzable group (X). Below, it is obtained by partially hydrolyzing the hydrolyzable organosilane.

The group R ³ in the hydrolyzable organosilane represented by the general formula (I) is the same or different and is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. 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;
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 and γ-chloropropyl group , 3,
Halogen-substituted hydrocarbon groups such as 3,3-trifluoropropyl group; substituted hydrocarbon groups such as γ-methacryloxypropyl group, γ-glycidoxypropyl group, 3,4-epoxycyclohexylethyl group, γ-mercaptopropyl group And the like. 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 includes, for example, an alkoxy group, an acetoxy group, an oxime group, an enoxy group, an amino group, an aminooxy group, an amide group and the like. Can be Among these, an alkoxy group is preferred because of its availability and ease of preparing the silica-dispersed oligomer solution (B).

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

Of the alkoxysilanes, in particular, m = 0
Examples of the tetraalkoxysilane include tetramethoxysilane and tetraethoxysilane. Examples of the organotrialkoxysilane having m = 1 include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, and phenyltrimethoxysilane. ,
Examples thereof include phenyltriethoxysilane and 3,3,3-trifluoropropyltrimethoxysilane. Further, as the diorganodialkoxysilane of m = 2,
Examples thereof include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane. Examples of the triorganoalkoxysilane having m = 3 include trimethylmethoxysilane, trimethylethoxysilane, and trimethylisopropoxysilane. And dimethylisobutylmethoxysilane. Further, an organosilane compound generally called a silane coupling agent is also included in the alkoxysilanes.

Of these hydrolyzable organosilanes represented by 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 drying and curing properties of the coating film tend to be poor. Colloidal silica in the silica-dispersed oligomer solution (B) has the effect of increasing the hardness of the cured coating applied with the inorganic coating and improving the smoothness and crack resistance. The colloidal silica is not particularly limited, and for example, water-dispersible or non-aqueous organic solvent-dispersible colloidal silica such as alcohol can be used. Generally, such colloidal silica is
It contains 20 to 50% by weight of silica as a solid content, and the silica content can be determined from this value. When using water-dispersible colloidal silica, water present as a component other than the solid content can be used for the hydrolysis of the hydrolyzable organosilane and used as a curing agent for the inorganic paint. it can. The water-dispersible colloidal silica is usually made of water glass, but can be easily obtained as a commercial product. The organic solvent-dispersible colloidal silica can be easily prepared by replacing 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 similarly to the water-dispersible colloidal silica. In the organic solvent-dispersible colloidal silica, the type of the organic solvent in which the colloidal silica is dispersed is not particularly limited. For example, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol and isobutanol; ethylene Ethylene glycol derivatives such as glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether acetate; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and diacetone alcohol. 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 and the like can also be used.

The colloidal silica in the silica-dispersed oligomer solution (B) has the above-mentioned effects. However, if the amount is too large, the cured film of the inorganic paint becomes too hard and causes cracks in the film. There is a possibility that. For this reason, in the silica-dispersed oligomer solution (B), the colloidal silica has a solid content of silica of 5 to 95% by weight (preferably 10 to 90% by weight, more preferably 20 to 90% by weight).
-85% by weight). When the content is less than 5% by weight, a desired coating hardness tends to be not obtained. On the other hand, if it exceeds 95% by weight, cracks are likely to occur.

As described above, the amount of water used for preparing the silica-dispersed oligomer solution (B) is 0.001 to 0.001 mol equivalent of the hydrolyzable group (X) of the hydrolyzable organosilane. It is in the range of 0.5 mole, preferably in the range of 0.01 to 0.4 mole. If the amount of water is less than 0.001 mol, a sufficient partial hydrolyzate cannot be obtained, and if it exceeds 0.5 mol, the stability of the partial hydrolyzate deteriorates. Here, the amount of water used in the partial hydrolysis reaction of the hydrolyzable organosilane is separately determined when colloidal silica containing no water (for example, colloidal silica using only an organic solvent as a dispersion medium) is used. It is the amount of water added. When colloidal silica containing water (for example, colloidal silica using only water or a mixed solvent of an organic solvent and water as a dispersion medium of colloidal silica) is used, It is the amount of water previously contained in at least the colloidal silica among the water previously contained and the water separately added. If the amount of water was previously contained in the colloidal silica alone and the amount used was sufficient, it was not necessary to separately add water, but the amount of water was previously contained in the colloidal silica. If water alone is not sufficient for the above usage, it is necessary to separately add water until the usage reaches the above usage. In this case, the amount of water used is the total amount of water previously contained in the colloidal silica and water added separately. In addition, even in the case where only the water previously contained in the colloidal silica is sufficient for the above use amount, water may be separately added, and in such a case, the use amount of the water is included in the colloidal silica in advance. It is the total amount of water added and water added separately. However, water is separately added so that the total amount does not exceed the upper limit (0.5 mol per 1 mol equivalent of the hydrolyzable group (X)).

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

The silica-dispersed oligomer solution (B) is adjusted to have a pH value in order to stably obtain its performance over a long period of time.
Preferably 2.0 to 7.0, more preferably 2.5 to
6.5, more preferably 3.0-6.0. If the pH is out of this range, the performance continuity of the component (B) is remarkably reduced particularly under the condition that the amount of water used is 0.3 mol or more per 1 mol equivalent of the hydrolyzable group (X). When the pH of the component (B) is outside the above range, the pH may be adjusted by adding a basic reagent such as ammonia or ethylenediamine if the pH is more acidic than the above range. The pH may be adjusted using an acidic reagent such as hydrochloric acid, nitric acid, and acetic acid. However, the adjustment method is not particularly limited.

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

R ⁴ in the above average composition formula (II) representing the silanol group-containing polyorganosiloxane in the component (C) is not particularly limited, and may be the same as R ³ in the above formula (I). Examples are preferably alkyl groups having 1 to 4 carbon atoms, phenyl group, vinyl group, γ-glycidoxypropyl group, γ-methacryloxypropyl group, γ-aminopropyl group, 3,3,3- It is a substituted hydrocarbon group such as a trifluoropropyl group, more preferably a methyl group and a phenyl group. Further, in the above formula (II), a and b are numbers satisfying the above-mentioned relationship, respectively. There are inconveniences. A is 2
When b is less than 4 and b is less than 0.0001, curing does not proceed well.

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

The component (D), ie, the curing catalyst (D), contained in the silicone resin (2) promotes the condensation reaction between the component (B) and the component (C), and forms a coating film of an inorganic coating having an antistatic function. Is a component that cures. Examples of the curing catalyst (D) include, but are not particularly limited to, 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; quaternary ammonium salts of carboxylic acids such as tetramethylammonium acetate; amines such as tetraethylpentamine; N-β-aminoethyl-γ-aminopropyltrimethoxysilane; N-β-amino Amine-based silane coupling agents such as ethyl-γ-aminopropylmethyldimethoxysilane; acids such as p-toluenesulfonic acid, phthalic acid and hydrochloric acid; aluminum compounds such as aluminum alkoxide and aluminum chelate; lithium acetate, lithium formate; Alkali metal salts such as sodium phosphate, potassium phosphate and potassium hydroxide; Titanium compounds such as tetraisopropyl titanate, tetrabutyl titanate and titanium tetraacetylacetonate; halogenated silanes such as methyltrichlorosilane, dimethyldichlorosilane and trimethylmonochlorosilane And the like.
However, other than these, there is no particular limitation as long as it is effective for accelerating the condensation reaction between the component (B) and the component (C).

The proportion of the components (B) and (C) in the silicone resin (2) is not particularly limited.
For example, in terms of the total solid content in terms of the total condensed compound,
For a total of 100 parts by weight of the components (B) and (C),
0.5-99.5 parts by weight of component (B), component 99.
5 to 0.5 part by weight is preferred, and component (B) 2.5 to 9
More preferably, 7.5 parts by weight, 97.5 to 2.5 parts by weight of the component (C), 5 to 95 parts by weight of the component (B), and 9 of the component (C)
5 to 5 parts by weight are more preferred. If the component (B) is less than 0.5 part by weight (the component (C) exceeds 99.5 parts by weight), the curability at room temperature tends to be poor, and sufficient film hardness tends not to be obtained. On the other hand, when the component (B) exceeds 99.5 parts by weight and the component (C) is less than 0.5 part by weight)
Curability is unstable, and a good coating film may not be obtained.

In the silicone resin (2), the mixing ratio of the component (D) is 100 parts by weight of the total solid content of the component (B) and the total solid content of the component (C). , 0.0001 to 10 parts by weight (preferably 0.0005 to 8 parts by weight, more preferably 0.0007 to 5 parts by weight). If the amount of (D) is less than 0.0001 part by weight, the room-temperature curability tends to decrease, and sufficient film hardness tends not to be obtained. 1
If the amount exceeds 0 parts by weight, the heat resistance and weather resistance of the cured film may be reduced, and the hardness of the cured film may be too high to cause cracks.

When the silicone resin contained in the antistatic function inorganic coating is the silicone resin (2), the antistatic function inorganic coating contains the hydrolyzable group of the organosilane oligomer contained in the component (B) and ( The silanol group of the polyorganosiloxane contained in the component (C) undergoes a condensation reaction when left at room temperature or heated at a low temperature in the presence of the curing catalyst (D) to form a cured film.
Therefore, such an antistatic inorganic coating is hardly affected by humidity even when it is cured at room temperature. Also,
Heat treatment can also promote the condensation reaction to form a cured film.

The curing accelerator contained in the inorganic coating is a component for accelerating the curing of the coating film (particularly, curing at normal temperature). Such a hardening accelerator is not particularly limited, but includes, for example, titanium oxide, zinc oxide, tin oxide, iron oxide, zirconium oxide, tungsten oxide, chromium oxide, molybdenum oxide, ruthenium oxide, germanium oxide, lead oxide, In addition to metal oxides such as cadmium oxide, copper oxide, vanadium oxide, niobium oxide, tantalum oxide, manganese oxide, cobalt oxide, rhodium oxide, nickel oxide, rhenium oxide, strontium titanate, etc. Is also preferable because it also has a photocatalytic action as an optical semiconductor. This optical semiconductor can also impart functionality such as antistatic properties to the inorganic coating film based on its inherent photocatalysis. Among these, the above-mentioned metal oxides are preferable in that they can be easily used practically, and among the metal oxides, titanium oxide is particularly preferable, and its curing acceleration performance, photocatalytic performance, safety, availability, and cost reduction. Preferred in terms of surface. When titanium oxide is used as a curing accelerator, it is better to use an anatase type (anatase type) as the crystal type because the curing acceleration performance and photocatalytic performance are the strongest, and the curing acceleration performance It is preferable in that the photocatalytic performance is expressed in a shorter time.

When transparency of the coating film is required, the average primary particle diameter of the curing accelerator is preferably 50 μm or less, more preferably 5 μm or less, and 0.5 μm or less.
More preferably, it is not more than μm. The curing accelerator is
One type may be used alone, or two or more types may be used in combination.

The curing accelerator may be in any form as long as it can be dispersed in the paint, such as powder, fine particle powder, and solution-dispersed sol particles. The curing proceeds in a shorter time, and is excellent in convenience for use. When a sol is used, the dispersion medium may be water or an organic solvent, but an organic solvent is preferable in terms of preparing a paint.

Further, the optical semiconductor referred to in the present specification includes a material which becomes a raw material of the optical semiconductor and a material which finally shows the properties of the optical semiconductor. The metal oxide and strontium titanate described above, in addition to the hardening promoting action,
It also has a photocatalytic action as an optical semiconductor (hereinafter, these may be referred to as a curing promoting optical semiconductor). It is known that an optical semiconductor generates active oxygen when irradiated with ultraviolet light (photocatalytic property). Since active oxygen can oxidize and decompose organic substances, its properties are used to make use of the properties of carbon-based dirt components attached to painted products (for example, carbon fractions contained in exhaust gas from automobiles, and dust from cigarettes). Self-cleaning effect to decompose, etc .; deodorant effect to decompose malodorous components represented by amine compounds and aldehyde compounds;
An antibacterial effect that prevents the generation of bacterial components represented by Staphylococcus aureus; a fungicidal effect and the like can be obtained. In addition, dirt such as organic substances repelling water adhered to the coating film surface is decomposed and removed by the photocatalytic action of the optical semiconductor, so that the wettability of the coating film with water is improved, and the anti-fog property and rainwater washing are performed. There is also an effect that antifouling property and the like can be obtained.

Further, the optical semiconductor also has an antistatic function by a photocatalytic action, and an antifouling effect can be obtained by this function. When the photo-semiconductor as a curing accelerator is irradiated with light on a coating film containing the same, the effect of the curing-promoting photo-semiconductor contained in the coating film reduces the surface resistance of the coating film, thereby exhibiting an antistatic effect. As a result, the coating film surface becomes less likely to become stained, and at the same time, the curing promotion action of the curing-promoting optical semiconductor increases the curing speed and the weather resistance of the film. When the optical semiconductor-containing coating film is irradiated with light, it is not yet clearly confirmed by what mechanism the surface resistance value of the coating film decreases or the curing of the coating film is accelerated,
It is considered that the electrons and holes generated by the light irradiation act on each other.

It is preferable that a metal is carried on the surface of the curing accelerator because the effect of promoting the curing is further enhanced. It is preferable that the curing accelerator is an optical semiconductor because the photocatalytic effect is further enhanced. Although the mechanism has not yet been clearly confirmed, the charge separation is promoted by supporting the metal on the surface of the curing accelerator,
This is considered to be related to the reduced probability of disappearance of electrons and holes generated by charge separation.

The metal which may be supported on the surface of the curing accelerator includes, for example, silver, copper, iron, nickel, zinc, platinum,
Gold, palladium, cadmium, cobalt, rhodium, ruthenium and the like are preferable in that charge separation of the curing accelerator is further promoted. The supported metal may be only one kind or two or more kinds. The amount of metal carried is not particularly limited,
For example, it is preferably 0.1 to 10% by weight, more preferably 0.2 to 5% by weight, based on the curing accelerator. If the loading is less than 0.1% by weight, the loading effect tends not to be sufficiently obtained. Problems tend to occur.

The method for supporting the metal is not particularly limited, and examples thereof include an immersion method, an impregnation method, and a photoreduction method. Moreover, you may use the clay crosslinked body which carried the hardening accelerator between layers. By introducing the curing accelerator between the layers, the curing accelerator is carried by the fine particles, and the curing acceleration effect and the photocatalytic performance are improved.

The amount of the curing accelerator in the inorganic coating is not particularly limited. For example, the curing accelerator is, for example, 100 parts by weight of the total of the solid content in terms of the total condensed compound and the total curing accelerator component in the total amount of the coating. When the metal is not supported on the surface of the curing accelerator, the amount is preferably 5 to 80 parts by weight, more preferably 10 to 50 parts by weight, and the metal is supported on the surface of the curing accelerator. If it is, preferably 2 to 75 parts by weight, more preferably 5 to 4 parts by weight
5 parts by weight. When the compounding amount of the curing accelerator is less than the above range, a sufficient curing promoting function (particularly, the curing promoting function at normal temperature) tends to be difficult to be obtained, and when it is more than the above range, cracks are easily generated. For example, the coating film performance tends to be reduced. In addition, when the metal is carried on the surface of the curing accelerator, the amount of the curing accelerator is not including the supported metal.

The inorganic paint can be toned by further containing a coloring agent such as a pigment or a dye, if necessary. The pigments that can be used are not particularly limited, but include, for example, organic pigments such as carbon black, quinacridone, naphthol red, cyanine blue, cyanine green, and Hansa yellow; titanium oxide, barium sulfate, red iron oxide, composite metal oxides, and the like. Inorganic pigments are preferred, and one or two or more selected from these groups may be used in combination. The dispersion of the pigment is not particularly limited, and may be a usual method, for example, a method of directly dispersing the pigment powder using a dyno meal, a paint shaker, or the like. At that time, a dispersant, a dispersing aid, a thickener, a coupling agent, and the like can be used. The amount of the pigment to be added is not particularly limited because the concealing property varies depending on the type of the pigment. Preferably 10
７０70 parts by weight. When the amount of the pigment is less than 5 parts by weight, the concealing property tends to be deteriorated, and when the amount is more than 80 parts by weight, the smoothness of the coating film may be deteriorated.

The dyes that can be used are not particularly limited, but include, for example, azo, anthraquinone, indicoid, sulfide, triphenylmethane, xanthene, alizarin, acridine, quinone imine,
And thiazole, methine, nitro and nitroso dyes. One kind selected from these groups or a combination of two or more kinds may be used. The amount of the dye added is not particularly limited because the concealing property varies depending on the type of the dye.
It is 80 parts by weight, more preferably 10 to 70 parts by weight.
When the amount of the dye is less than 5 parts by weight, the concealing property tends to be deteriorated, and when it exceeds 80 parts by weight, the smoothness of the coating film may be deteriorated.

Note that a leveling agent, metal powder, glass powder,
Antibacterial agents, antioxidants, ultraviolet absorbers and the like may also be included in the antistatic inorganic coating within a range that does not adversely affect the effects of the present invention. The inorganic paint can be used by diluting it with various organic solvents, if necessary, because of the ease of handling, or may be diluted with the same organic solvent. The type of the organic solvent can be appropriately selected according to the type of the monovalent hydrocarbon group contained in each component of the silicone resin, the molecular weight of each component of the silicone resin, and the like.
Such an organic solvent is not particularly limited,
For example, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol and isobutanol; ethylene glycol derivatives such as ethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether; diethylene glycol such as diethylene glycol and diethylene glycol monobutyl ether Derivatives; and toluene,
Xylene, hexane, heptane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, diacetone alcohol and the like can be mentioned, and one or more selected from the group consisting of these can be used. it can. The dilution ratio in the organic solvent is not particularly limited, and the dilution ratio may be appropriately determined as needed.

The method for applying the inorganic paint is not particularly limited. For example, there can be used various ordinary coating methods such as brush coating, spraying, dipping (dipping), roll, flow, curtain, knife coating and spin coating. You can choose. The method for curing the coating film of the inorganic paint may be a known method, and is not particularly limited.
The temperature at the time of curing is not particularly limited, either, and may be in a wide range from room temperature to heating temperature according to the desired performance of the cured film and the heat resistance of the curing accelerator.

The thickness of the cured coating film formed from the inorganic paint is not particularly limited, and is, for example, 0.05 to 10 μm.
As long as it is sufficient, the antistatic function is more effectively exerted and the curing time at room temperature is shortened, and the applied cured film is stably adhered and held for a long time, and cracks and peeling To prevent the occurrence of
5 μm is preferable, and 0.05 to 2 μm is more preferable.

The substrate to be coated by the low-temperature curing inorganic coating method of the present invention is not particularly limited, and examples thereof include an inorganic substrate, an organic substrate, an inorganic-organic composite substrate, and any one of these. And a coating substrate having at least one inorganic coating film and / or at least one organic coating film on the surface thereof. The inorganic substrate is not particularly limited, for example, a metal substrate; a glass substrate;
Enamel; inorganic building materials such as water glass decorative boards and inorganic cured products; and ceramics.

The metal substrate is not particularly limited. For example, a non-ferrous metal [eg, aluminum (J
IS-H4000 etc.), aluminum alloys (duralumin etc.), copper, zinc etc.), iron, steel [for example, rolled steel (J
IS-G3101 etc.), hot-dip galvanized steel (JIS-G
3302 etc.), (rolled) stainless steel (JIS-G43
04, G4305 etc.), tinplate (JIS-G330)
3) and other general metals (including alloys).

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

The water glass decorative board refers to, for example, a decorative board obtained by applying sodium silicate to a cement base such as a slate and baking it. The inorganic hardened material is not particularly limited. For example, a fiber reinforced cement board (J
IS-A5430, etc.), ceramic siding (JIS-
A5422), wood wool cement board (JIS-A5404)
Pulp cement board (JIS-A5414 etc.), slate / wood wool cement laminate board (JIS-A5426)
Gypsum board products (JIS-A6901 etc.), clay roof tiles (JIS-A5208 etc.), thick slate (JIS-A6901 etc.)
A5402), ceramic tile (JIS-A5209)
Etc.), concrete blocks for construction (JIS-A540)
6), terrazzo (JIS-A5411, etc.), prestressed concrete double T slab (JIS-A5412)
Etc.), ALC panel (JIS-A5416 etc.), hollow prestressed concrete panel (JIS-A6511)
Etc.), and all types of base materials obtained by curing and molding inorganic materials such as ordinary bricks (JIS-R1250 etc.).

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

The inorganic-organic composite base material is not particularly limited.
Fiber reinforced plastics (FRP) reinforced with inorganic fibers such as carbon fibers, and the like. The organic film constituting the coating substrate is not particularly limited, for example, acrylic, alkyd, polyester, epoxy, urethane, acrylic silicone, chlorinated rubber, phenol, melamine, etc. A cured film of a coating material containing an organic resin may be used.

The inorganic coating constituting the coating substrate is not particularly limited, and includes, for example, a cured coating of a coating material containing an inorganic resin such as a silicone resin. When applying the inorganic paint to the substrate in the present invention, depending on the material and surface state of the substrate, it may be difficult to obtain adhesion and weather resistance if the inorganic paint is applied as it is, if necessary, the base material A primer layer may be formed on the surface in advance. Organic, as primer layer
Regardless of inorganic, although not particularly limited, examples of the organic primer layer include a nylon resin, an alkyd resin, an epoxy resin, an acrylic resin, an organic modified silicone resin (for example, an acrylic silicone resin), a chlorinated rubber resin, and a urethane resin. At least one selected from the group consisting of phenolic resin, polyester resin and melamine resin
Examples of the inorganic primer layer include a cured resin layer of an organic primer composition containing 10% by weight or more of a kind of organic resin as a solid content, and an example of an inorganic primer layer containing 90% by weight or more of an inorganic resin such as a silicone resin as a solid content. And a cured resin layer of an inorganic primer composition.

The thickness of the primer layer is not particularly limited, but is preferably, for example, 0.1 to 50 μm, and 0.5 to 50 μm.
-10 μm is more preferred. If the thickness is too small, adhesion and weather resistance may not be obtained. If the thickness is too large, foaming may occur during drying. A substrate having at least one organic primer layer and / or inorganic primer layer on its surface is included in the category of the coated substrate. That is, the coating film on the surface of the coating substrate may be the primer layer.

The primer layer may contain a coloring agent such as a pigment or a dye for toning, if necessary. Examples of the colorant that can be used include those described above as those that can be added to the inorganic paint. The preferred numerical range of the amount of the coloring agent to be added to the primer layer is the same as in the case of the above-mentioned inorganic paint. However, the amount is specified not with respect to 100 parts by weight of the solid content in terms of the total condensed compound, but with respect to 100 parts by weight of the total resin solid content in the total amount of the primer composition.

The form of the substrate is not particularly limited, and examples thereof include a film, a sheet, a plate, and a fiber. Further, the base material may be a molded body of a material having these shapes, or a structure partially provided with at least one of the material having the shape or the molded body. The base material may be made of the above-mentioned various materials alone, a composite material obtained by combining at least two of the above-described various materials, or a laminated material obtained by laminating at least two of the above-described various materials. May be.

In the coated product obtained by the coating method of the present invention, since a curing accelerator is added to the inorganic coating, the curing of the coating film proceeds in a short time and the weather resistance of the coating film is enhanced. for that reason,
By equipping at least a part of various materials or articles with this cured film, for example, it can be suitably used for the following applications. Building-related members or articles, for example, exterior materials (eg, exterior wall materials, flat tiles, Japanese tiles, metal tiles, etc.), resin rain gutters such as PVC rain gutters, and metal rain gutters such as stainless steel gutters. Such as rain gutters, gates and members for use therewith (eg, gates, gateposts, gate walls, etc.), fences (fences) and members for use therewith,
Garage doors, home terraces, doors, pillars, car ports, bicycle parking ports, sign posts, home delivery posts, wiring boards such as switchboards and switches, gas meters, intercoms, TV doorphones and camera lens parts, electric locks, entrance poles, porch Windows (eg, daylighting windows, skylights, open / close windows such as louvers, etc.) and members for use therewith (eg, window frames,
Shutters, blinds, etc.), automobiles, railway vehicles, aircraft, ships, machinery, road peripherals (for example, soundproof walls, tunnel interior boards, various display devices, guardrails, bollards, railing, traffic signposts and signposts, Traffic lights, post cones, etc., advertising towers, outdoor or indoor lighting fixtures and members for use therewith (for example, members made of at least one material selected from the group consisting of glass, resin, metal and ceramics) ), Glass for solar cells,
Agricultural vinyl and glass houses, outdoor units for air conditioners, antennas for VHF, UHF, BS, CS, etc.

The above-mentioned inorganic paint may be directly applied to at least a part of the above-mentioned various materials or articles and cured, but is not limited thereto. Alternatively, the cured antistatic function film may be attached to at least a part of the above-mentioned various materials or articles. As the material of the base material of such a film, for example, polyethylene terephthalate (PET) resin, polybutylene terephthalate (PB)
T) Resins such as a resin, a vinyl chloride resin, an acrylic resin, a fluororesin, a polypropylene (PP) resin, and a composite resin thereof, but are not particularly limited.

[0069]

The present invention will be described in detail below with reference to examples and comparative examples. In Examples and Comparative Examples, all “parts” represent “parts by weight” and all “%” represent “% by weight” unless otherwise specified. The molecular weight is measured by GPC (gel permeation chromatography) using HLC8020 manufactured by Tosoh Corporation as a measurement model, using a standard polystyrene as a calibration curve, and calculating the converted value. In addition, this invention is not limited to a following example. 100 parts of methyltrimethoxysilane <Example 1> material (A _1), the raw material (A ₂₎ as 10 parts tetraethoxysilane, also raw material (A ₂₎ as IPA organosilica sol is acidic colloidal silica (trade name " OS
CAL1432 ", manufactured by Catalyst Kasei Kogyo Co., Ltd., solid content 30
%), 30 parts of dimethyldimethoxysilane as a raw material (A ₃ ), 100 parts of isopropyl alcohol (hereinafter abbreviated as IPA) as a diluent, and 90 parts of water.
Was added and stirred. The obtained liquid was heated in a 60 ° C. constant temperature bath for 5 hours to adjust the weight average molecular weight (Mw) of the organosiloxane (A) as a reaction product to 1500 to obtain an alcohol solution of the organosiloxane.

Preparation conditions of alcohol solution of organosiloxane: [Water] / [OR ¹ ] molar ratio 1.73 Weight-average molecular weight 1500 Solid content in terms of total condensed compound 23.3% Titanium oxide sol (Titanium oxide sol manufactured by Catalysis Chemical Co., Ltd .: trade name "Queen Titanic 11-1020G") was added to 100 parts in total of the total solid content in terms of the total condensed compound and the total curing accelerator component in the total amount of the paint. The inorganic coating material (1) was obtained by adding and mixing the curing accelerator in an amount of 20 parts.

The inorganic coating material (1) was applied to a glass substrate washed with acetone by a spray coating method, and the coating film was dried and cured at room temperature to obtain a coated product (1).
The cured film had a thickness of 0.5 μm. The curing time at room temperature was examined by measuring room temperature curing performance described below (the same applies hereinafter). <Example 2> The procedure of Example 1 was repeated, except that the same amount of titanium oxide powder (titanium oxide manufactured by Ishihara Sangyo Co., Ltd .: trade name “ST-01”) was used as a curing accelerator instead of titanium oxide sol. Inorganic paint (2) as in Example 1
I got

The inorganic coating material (2) was applied to a glass substrate washed with acetone by a spray coating method, and the coating film was dried and cured at room temperature to obtain a coated product (2).
The cured film had a thickness of 0.5 μm. <Example 3> An inorganic coating material (3) was obtained in the same manner as in Example 1, except that the same amount of titanium oxide supporting platinum was used instead of the titanium oxide sol as a curing accelerator.

The platinum was loaded on a titanium oxide powder (titanium oxide manufactured by Ishihara Sangyo Co., Ltd .: trade name “ST-01”) by a photoelectrodeposition method, and 0.5% was loaded on the titanium oxide.
Next, the inorganic coating material (3) was applied to the glass substrate washed with acetone by a spray coating method, and the coating film was dried and cured at room temperature to obtain a coated product (3). The cured film had a thickness of 0.5 μm. <Example 4> A coated product (4) was obtained in the same manner as in Example 1, except that an aluminum substrate was used instead of the glass substrate as the base material. Example 5 100 parts of methyltrimethoxysilane as a raw material (A ₁ ) and IPA organosilica sol (trade name “OSC”) as an acidic colloidal silica as a raw material (A ₂ )
AL1432 ", manufactured by Sekiyu Kasei Kogyo Co., Ltd., solid content 30
%), 30 parts of dimethyldimethoxysilane as a raw material (A ₃ ), and 100 parts of IPA as a diluting solvent were mixed,
Further, 120 parts of water was added and stirred. 6
By heating for 5 hours in a thermostat at 0 ° C., the weight average molecular weight (Mw) of the organosiloxane (A) as a reaction product is increased.
Was adjusted to 1200 to obtain an alcohol solution of an organosiloxane.

Preparation conditions of alcohol solution of organosiloxane: [Water] / [OR ¹ ] molar ratio 2.46 ・ Weight average molecular weight 1200 ・ Solid content in terms of all condensed compounds 20.9% Titanium oxide sol (Titanium oxide sol manufactured by Catalyst Chemicals, Inc .: trade name "Queen Titanic 11-1020G") is cured for a total of 100 parts of the total solid content in terms of all condensed compounds and the total curing accelerator in the total amount of paint. By adding and mixing the amount of the accelerator to be 20 parts,
An inorganic paint (5) was obtained.

The inorganic coating (5) was applied to a glass substrate washed with acetone by a spray coating method, and the coating was dried and cured at room temperature to obtain a coated product (5).
The cured film had a thickness of 0.5 μm. <Example 6> A coated product (6) was obtained in the same manner as in Example 5, except that an aluminum substrate was used instead of the glass substrate as the base material. <Example 7> A coated product (7) was obtained in the same manner as in Example 5, except that an acrylic substrate was used instead of the glass substrate as the base material. <Example 8> An inorganic paint (8) was obtained in the same manner as in Example 5, except that the addition amount of the titanium oxide sol used as the curing accelerator was changed to 5 parts.

The inorganic coating material (8) was applied to an aluminum substrate washed with acetone by a spray coating method, and the coating film was dried and cured at room temperature to obtain a coated product (8).
The cured film had a thickness of 0.5 μm. <Example 9> An inorganic paint (9) was obtained in the same manner as in Example 5, except that the addition amount of the titanium oxide sol used as the curing accelerator was changed to 80 parts.

The inorganic coating (9) was applied to a glass substrate washed with acetone by a spray coating method, and the coating was dried and cured at room temperature to obtain a coated product (9).
The cured film had a thickness of 0.5 μm. 100 parts of methyltrimethoxysilane as <Example 10> material (A _1), the raw material (A ₂₎ as 20 parts tetraethoxysilane, also raw material (A ₂₎ as IPA organosilica sol is acidic colloidal silica (trade name " O
SCAL1432 ", manufactured by Catalyst Chemical Industry Co., Ltd., solid content 3
(0%), 50 parts of dimethyldimethoxysilane as a raw material (A ₃ ), and 100 parts of IPA as a diluting solvent, and further, 180 parts of water were added and stirred. The obtained liquid was heated in a 60 ° C. constant temperature bath for 5 hours to obtain a weight average molecular weight (M) of the organosiloxane (A) as a reaction product.
The value of w) was adjusted to 1200 to obtain an organosiloxane alcohol solution.

Preparation conditions of alcohol solution of organosiloxane: [Water] / [OR ¹ ] molar ratio 2.92 ・ Weight average molecular weight 1200 ・ Solid content in terms of total condensed compound 20.2% Titanium oxide sol (Titanium oxide sol manufactured by Ishihara Sangyo Co., Ltd .: trade name "STS-01")
Was added in an amount of 20 parts of the curing accelerator to 100 parts of the total of the solid content in terms of the total condensed compound and the total curing accelerator in the total amount of the coating to obtain an inorganic coating (10).

The inorganic coating material (10) was applied to a glass substrate washed with acetone by a spray coating method, and the coating film was dried and cured at room temperature to obtain a coated product (10). The cured film had a thickness of 0.5 μm. 100 parts of methyltrimethoxysilane as <Example 11> material (A _1), the raw material (A ₂₎ as 10 parts tetraethoxysilane, also raw material (A ₂₎ as IPA organosilica sol is acidic colloidal silica (trade name " O
SCAL1432 ", manufactured by Catalyst Chemical Industry Co., Ltd., solid content 3
(0%), 90 parts of IPA and 100 parts of IPA as a diluting solvent were further added, and 200 parts of water was further added and stirred. The obtained liquid was heated in a 60 ° C. constant temperature bath for 5 hours to obtain a weight average molecular weight (M) of the organosiloxane (A) as a reaction product.
The value of w) was adjusted to 1200 to obtain an organosiloxane alcohol solution.

Preparation conditions of alcohol solution of organosiloxane: [Water] / [OR ¹ ] molar ratio 4.63 ・ Weight average molecular weight 1200 ・ Solid content in terms of total condensed compound 15.8% Titanium oxide sol (Titanium oxide sol manufactured by Ishihara Sangyo Co., Ltd .: trade name "STS-01")
Was added and mixed in such an amount that the curing accelerator was 20 parts with respect to 100 parts in total of the total solid content in terms of the total condensed compound and the total curing accelerator in the total amount of the coating, thereby obtaining an inorganic coating (11).

The inorganic coating material (11) was applied to a glass substrate washed with acetone by a spray coating method, and the coating film was dried and cured at room temperature to obtain a coated product (11). The cured film had a thickness of 0.5 μm. Example 12 100 parts of methyltrimethoxysilane as a raw material (A ₁ ) and IPA organosilica sol (trade name “OS”) as an acidic colloidal silica as a raw material (A ₂ )
CAL1432 ", manufactured by Catalyst Kasei Kogyo Co., Ltd., solid content 30
%), 100 parts of IPA as a diluting solvent were mixed,
Further, 60 parts of water was added and stirred. The obtained liquid is
The mixture was heated in a constant temperature bath at 5 ° C. for 5 hours to adjust the weight average molecular weight (Mw) of the organosiloxane (A) as a reaction product to 950 to obtain an alcohol solution of the organosiloxane.

Preparation conditions of alcohol solution of organosiloxane: [Water] / [OR ¹ ] molar ratio 1.51 ・ Weight average molecular weight 950 ・ Solid content in terms of total condensed compound 21.0% Titanium oxide sol (Titanium oxide sol manufactured by Catalyst Chemicals, Inc .: trade name "Queen Titanic 11-1020G") is cured for a total of 100 parts of the total solid content in terms of all condensed compounds and the total curing accelerator in the total amount of paint. By adding and mixing the amount of the accelerator to be 20 parts,
An inorganic paint (12) was obtained.

The inorganic coating material (12) was applied to a glass substrate washed with acetone by a spray coating method, and the coating film was dried and cured at room temperature to obtain a coated product (12). The cured film had a thickness of 0.5 μm. <Example 13> A coated product (13) was obtained in the same manner as in Example 12, except that the film thickness after curing of the coating film was changed to 1.0 µm. <Example 14> In Example 12, the coating method was changed to the spin coating method, and the film thickness after curing of the coating film was changed to 0.05 μm.
Except having changed to m, the same operation as Example 12 was performed to obtain a coated product (14). <Example 15> In Example 12, the coating method was changed to spin coating to change the coating film thickness after curing to 0.1 μm.
The same operation as in Example 12 was carried out, except that the coating product (15) was obtained. <Example 16> A coated product (16) was obtained in the same manner as in Example 12, except that the film thickness after curing of the coating film was changed to 0.3 µm. <Example 17> In Example 12, the inorganic paint (12) was used.
To this was added 45 parts of a pigment (white pigment manufactured by Ishihara Sangyo Co., Ltd.) based on 100 parts of the total solid content in terms of the total condensed compound in the total amount of the paint to obtain an inorganic paint (17).

The inorganic coating (17) was applied to a glass substrate washed with acetone by a spray coating method, and the coating was dried and cured at room temperature to obtain a coated product (17). The cured film had a thickness of 0.5 μm. Comparative Example 1 A comparative inorganic paint (1) was obtained in the same manner as in Example 1, except that the addition amount of the titanium oxide sol used as the curing accelerator was changed to 0.5 part.

The comparative inorganic coating material (1) was applied to a glass substrate washed with acetone by a spray coating method, and the coating film was dried and cured at room temperature to obtain a comparative coated product (1). In addition, the thickness of the cured film is 0.5 μm.
Met. Comparative Example 2 A comparative inorganic paint (2) was obtained in the same manner as in Example 5, except that the addition amount of the titanium oxide sol used as the curing accelerator was changed to 85 parts.

The comparative inorganic coating material (2) was applied to an aluminum substrate washed with acetone by a spray coating method, and the coating film was dried and cured at room temperature to obtain a comparative coated product (2). In addition, the thickness of the cured film is 0.5 μm.
Met. <Comparative Example 3> In Example 1, a commercially available low-temperature curing agent (carbon black manufactured by Lion Corporation; trade name "Oil Furnace Carbon FP-C") was used in place of the titanium oxide sol used as a curing accelerator in the total amount of the paint. 50 parts per 100 parts of the total solid content in terms of the total condensed compound and the low-temperature curing agent
A comparative inorganic coating material (3) was obtained in the same manner as in Example 1 except that part was used.

The comparative inorganic coating material (3) was applied to a glass substrate washed with acetone by a spray coating method, and the coating film was dried and cured at room temperature to obtain a comparative coated product (3). In addition, the thickness of the cured film is 0.5 μm.
Met. 100 parts of methyltrimethoxysilane <Example a> material (A _1), the raw material (A ₂₎ as 10 parts tetraethoxysilane, also raw material (A ₂₎ as IPA organosilica sol is acidic colloidal silica (trade name " OS
CAL1432 ", manufactured by Catalyst Kasei Kogyo Co., Ltd., solid content 30
%), 100 parts of isopropyl alcohol (hereinafter abbreviated as IPA) as a diluting solvent, and
Was added and stirred. The obtained liquid was heated in a 60 ° C. constant temperature bath for 5 hours to adjust the weight average molecular weight (Mw) of the organosiloxane (A) as a reaction product to 1,000, thereby obtaining an alcohol solution of the organosiloxane.

Preparation conditions of alcohol solution of organosiloxane: [Water] / [OR ¹ ] molar ratio 2.08 ・ Weight average molecular weight 1000 ・ Solid content in terms of total condensed compound 20.3% Titanium oxide sol (Titanium oxide sol manufactured by Catalyst Chemicals, Inc .: trade name "Queen Titanic 11-1020G") is cured for a total of 100 parts of the total solid content in terms of all condensed compounds and the total curing accelerator in the total amount of paint. By adding and mixing the amount of the accelerator to be 20 parts,
An inorganic paint (a) was obtained. <Comparative Example 4> The inorganic coating material (a) obtained in Example a was applied to a glass substrate washed with acetone by a spin coating method, and the coating film was dried and cured at room temperature. ) Got. In addition, the film thickness after curing of the coating film is 0.1.
03 μm. <Comparative Example 5> The inorganic paint (a) obtained in Example a was applied to a glass substrate washed with acetone by a spray coating method, and the coating film was dried and cured at room temperature to obtain a comparative coated product (5). I got The cured film had a thickness of 15 μm.

Next, prior to the following examples and comparative examples, the silicone resin (2) (B),
(C) The component was prepared as follows. (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%, moisture 0.5%, manufactured by Nissan Chemical Industries, Ltd.)
100 parts, 68 parts of methyltrimethoxysilane, and 1 part of water
0.8 parts, and the mixture was subjected to a partial hydrolysis reaction at 65 ° C. for about 5 hours with stirring, followed by cooling to obtain a silica-dispersed oligomer solution of organosilane. This is called B-1. This had a solid content of 36% in terms of total condensed compounds when left at room temperature for 48 hours.

Preparation conditions of B-1:-Number of moles of water per mole equivalent of hydrolyzable group: 0.4 mole-Silica content of component (B-1): 47.2%-Hydrolysis with m = 1 % Of the soluble organosilane 100% by mole <Preparation Example B-2> Colloidal silica sol XBA-S dispersed in a xylene / n-butanol mixed solvent in a flask equipped with a stirrer, a heating jacket, a condenser and a thermometer.
T (particle diameter 10 to 20 nm, solid content 30%, moisture 0.2
%, Manufactured by Nissan Chemical Industry Co., Ltd.) and 68 parts of methyltrimethoxysilane, and a partial hydrolysis reaction was carried out at 65 ° C. for about 5 hours with stirring, followed by cooling. An organosilane silica-dispersed oligomer solution was obtained. This is called B-2. This product has a solid content in terms of total condensed compounds of 3 hours when left at room temperature for 48 hours.
It was 7.8%.

Preparation conditions of B-2:-Number of moles of water per mole equivalent of hydrolyzable group 0.007 moles-Content of silica component (B-2) 47.2%-Hydrolysis of m = 1 Preparation Example B-3> 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%, moisture 0.5%, manufactured by Nissan Chemical Industries, Ltd.)
100 parts, 68 parts of methyltrimethoxysilane, 18 parts of dimethyldimethoxysilane, 2.7 parts of water, and 0.1 part of acetic anhydride are charged, and the mixture is partially hydrolyzed at 80 ° C. for about 3 hours while stirring. After the decomposition reaction, the mixture was cooled to obtain a silica-dispersed oligomer solution of organosilane. This is called B-3. It had a solid content of 39.5% in terms of total condensed compounds when left at room temperature for 48 hours.
Met.

Preparation conditions of B-3:-Number of moles of water per mole equivalent of hydrolyzable group: 0.1 mole-Silica content of component (B-3): 40.2%-Hydrolysis of m = 1 % Of the soluble organosilane 77% by mole (Preparation example of component C): <Preparation example C-1> 220 parts of methyltriisopropoxysilane in a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel and a thermometer. (1 mol) was dissolved in 150 parts of toluene.
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 dropwise addition, the stirring was stopped, and the reaction solution was transferred to a separating funnel and allowed to stand, and then separated into two layers.
The mixed solution of the lower layer of water and isopropyl alcohol containing a small amount of hydrochloric acid was separated and removed, the remaining hydrochloric acid in the remaining toluene resin solution was removed by washing with water, and toluene was further removed under reduced pressure. By diluting the product with isopropyl alcohol, a weight average molecular weight (Mw) of about 200
Thus, an isopropyl alcohol solution of the silanol group-containing polyorganosiloxane was obtained. This is called C-1.
The solid content of this solution C-1 in terms of the total condensed compound is 40%. It has also been confirmed that the silanol group-containing polyorganosiloxane in C-1 satisfies the above average composition formula (II).

<Preparation Example C-2> 1000 parts of water and 50 parts of acetone were charged into a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel, and a thermometer, and further 44.8 parts of methyltrichlorosilane (0.4%). 38.7 parts), 38.7 parts (0.3 mol) of dimethyldichlorosilane and 84.6 parts (0.
(4 mol) dissolved in 200 parts of toluene was hydrolyzed at 60 ° C. while dropwise adding a solution with stirring. Forty minutes after the completion of the dropwise addition, the stirring was stopped, and the reaction solution was transferred to a separating funnel and allowed to stand, and then separated into two layers. The lower layer of aqueous hydrochloric acid is separated and the remaining water and hydrochloric acid remaining in the toluene solution of organopolysiloxane are removed together with excess toluene by vacuum stripping to obtain a weight average molecular weight (Mw) of about 3,000. A toluene solution of the silanol group-containing polyorganosiloxane was obtained. This is C
-2. The solid content in terms of the total condensed compound in this solution C-2 is 60%. It has also been confirmed that the silanol group-containing polyorganosiloxane in C-2 satisfies the above average composition formula (II).

(B) and (C) obtained as described above.
The following Examples and Comparative Examples were performed using the components. Example 18 B-1 (70 parts (about 25 parts in terms of total condensed compound equivalent solids)), C-1 (30 parts (12 parts in terms of total condensing compound equivalent solids)) and curing catalyst N
After mixing with 1 part of -β-aminoethyl-γ-aminopropylmethyldimethoxysilane, titanium oxide sol (Titanium oxide sol manufactured by Catalysis Kasei Co., Ltd .: trade name “Queen Titanic 11-1020G”) was used as a curing accelerator. An inorganic coating material (18) was obtained by adding and mixing the hardening accelerator in an amount of 10 parts based on 100 parts of the total solid content in terms of the total condensed compound and the hardening accelerator in the total amount of the coating material.

The inorganic paint (18) is applied to a stainless steel substrate washed with acetone by a spray coating method, and the coated film is dried and cured at room temperature to obtain a coated product (18).
I got The cured film had a thickness of 1.0 μm. <Example 19> The procedure of Example 18 was carried out except that the same amount of titanium oxide powder (titanium oxide manufactured by Ishihara Sangyo Co., Ltd .: trade name "ST-01") was used as a curing accelerator instead of titanium oxide sol. In the same manner as in Example 18, an inorganic paint (19) was obtained.

The inorganic paint (19) is applied to a stainless steel substrate washed with acetone by a spray coating method, and the coating film is dried and cured at room temperature to obtain a coated product (19).
I got The cured film had a thickness of 1.0 μm. <Example 20> An inorganic paint (20) was obtained in the same manner as in Example 18, except that the same amount of titanium oxide supporting silver was used instead of the titanium oxide sol.

The silver was carried on the titanium oxide powder (titanium oxide manufactured by Ishihara Sangyo Co., Ltd .: trade name "STS-01") by the photoelectrodeposition method, and 0.5% was carried on the titanium oxide.
Next, the inorganic coating material (20) was applied to the glass substrate washed with acetone by a spray coating method, and the coating film was dried and cured at room temperature to obtain a coated product (20). In addition,
The film thickness after curing of the coating film was 0.5 μm. <Example 21> Titanium oxide powder (Titanium oxide manufactured by Ishihara Sangyo Co., Ltd .: trade name: ST) in B-2 (60 parts (about 23 parts in terms of total condensed compound equivalent solids)) as a curing accelerator
-01 "), the curing accelerator is 10 per 100 parts of the total of the solid content in terms of the total condensed compound and the curing accelerator in the total amount of the paint.
Parts, a solution obtained by dispersing, C-1 (40 parts (16 parts as a solid content in terms of total condensation compound)), and N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane as a curing catalyst By mixing the two parts
An inorganic paint (21) was obtained.

This inorganic coating (21) was applied to a glass substrate washed with acetone by a spray coating method, and the coating was dried and cured at room temperature to obtain a coated product (21). The cured film had a thickness of 0.1 μm. <Example 22> Titanium oxide sol (Titanium oxide sol manufactured by Ishihara Sangyo Co., Ltd.) as a curing accelerator in B-1 (60 parts (about 23 parts in terms of total condensed compound equivalent solids))
A solution obtained by dispersing TS-01 ”) in an amount of 10 parts of the curing accelerator to 100 parts in total of the solid content in terms of the total condensed compound and the curing accelerator in the total amount of the coating material, and C-1 ( 40
(In terms of the total condensed compound equivalent: 16 parts)) and 2 parts of N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane as a curing catalyst to obtain an inorganic coating (22). .

The inorganic coating (22) was applied to a glass substrate washed with acetone by a spray coating method, and the coating was dried and cured at room temperature to obtain a coated product (22). The cured film had a thickness of 0.3 μm. <Example 23> B-2 (50 parts (about 19 parts in terms of total condensed compound equivalent solids)), C-2 (50 parts (30 parts in terms of total condensing compound equivalent solids)) and curing catalyst After mixing 2 parts of N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane as a curing accelerator, titanium oxide sol (Titanium oxide sol manufactured by Catalyst Kasei Co., Ltd .: trade name “Queen Titanic 11-1020G”) ),
An inorganic paint (23) was obtained by adding and mixing an amount of 5 parts of the curing accelerator to 100 parts of the total of the solid content in terms of the total condensation compound and the curing accelerator in the total amount of the coating.

This inorganic paint (23) is applied to a glass substrate washed with acetone by a spin coating method, and the coating film is dried and cured at room temperature to obtain a coated product (23).
I got The cured film had a thickness of 0.05 μm. <Example 24> B-3 (50 parts (about 20 parts in terms of total condensed compound equivalent solids)), C-2 (50 parts (in terms of total condensing compound equivalent solids 30 parts)), and curing catalyst After mixing 2 parts of N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane as a curing accelerator, titanium oxide sol (Titanium oxide sol manufactured by Catalyst Kasei Co., Ltd .: trade name “Queen Titanic 11-1020G”) ),
An inorganic paint (24) was obtained by adding and mixing an amount of 5 parts of the curing accelerator to 100 parts of the total of the solid content in terms of the total condensed compound and the curing accelerator in the total amount of the coating.

The inorganic coating (24) was applied to a glass substrate washed with acetone by a spray coating method, and the coating was dried and cured at room temperature to obtain a coated product (24). The cured film had a thickness of 0.2 μm. <Example 25> An epoxy-based primer (Isamu Paint Co., Ltd .: trade name "E-1") was applied to the surface of a glass plate washed with acetone.
Primer ") was applied to a thickness of about 10 μm, and then the inorganic coating (1) obtained in Example 1 was cured to a thickness of 0.1 μm.
By spray coating, and then dried and cured at room temperature to obtain a coated product (25). <Example 26> An epoxy-based primer (Isamu Paint Co., Ltd .: trade name "E-
1 Primer ") was applied to a thickness of about 10 μm, and then the inorganic coating (18) obtained in Example 18 was cured to a thickness of 0.1 μm.
It was applied by a spray coating method so as to have a thickness of 1 μm, and then dried and cured at room temperature to obtain a coated product (26). <Example 27> First, a primer composition (27
Components -1) to (27-4) were prepared as follows.

Preparation of component (27-1): 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%, moisture: 0%) 0.5%, manufactured by Nissan Chemical Industry Co., Ltd.), 68 parts of methyltrimethoxysilane, and 2.2 parts of water 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-dispersed oligomer solution of organosilane was obtained. This is called a (27-1) component.
This product had a solid content of 37.3% in terms of total condensed compounds when left at room temperature for 48 hours.

Preparation conditions of component (27-1): 0.1 mole of water per 1 mole equivalent of hydrolyzable group 0.1% silica content of component (27-1) 47.3% m = 1 (27-2) Component: 40% solution of a silanol group-containing polyorganosiloxane having a weight average molecular weight (Mw) of about 2,000 obtained in Preparation Example C-1 and a 40% solution of isopropyl alcohol. C-1 is referred to as a component (27-2).

Component (27-3): As the component (27-3), N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane is referred to as D-1 and dibutyltin dilaurate is referred to as D-2. (27-4) Preparation of Component: Next, in a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel, a nitrogen gas inlet / outlet, and a thermometer, 5.69 parts of n-butyl methacrylate (BMA). (40 mmol), trimethoxysilylpropyl methacrylate (SMA)
1.24 parts (5 mmol), 0.71 part (5 mmol) of glycidyl methacrylate (GMA), and 0.1% of γ-mercaptopropyltrimethoxysilane as a chain transfer agent.
A reaction solution obtained by dissolving 784 parts (4 mmol) in 8.49 parts of toluene was added with azobisisobutyronitrile 0.0
A solution obtained by dissolving 25 parts (0.15 mmol) in 3 parts of toluene was dropped under a nitrogen stream, and reacted at 70 ° C. for 2 hours. Thus, a 40% toluene solution of an acrylic resin having a weight average molecular weight Mw = 1000 was obtained. This is (27
-4) called a component.

Preparation conditions of component (27-4): monomer molar ratio BMA / SMA / GMA = 8/1 /
1. Weight average molecular weight 1000 Solid content 40% And the solid content is 25 with isopropyl alcohol.
% To obtain a primer composition. This primer composition was coated on an acrylic plate (50 mm
(× 50 mm × 2.5 mm) by a spray coating method so as to have 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, a setting time of 10 minutes is allowed, and the inorganic coating (24) obtained in Example 24 is applied by a spray coating method so as to have a cured coating thickness of 0.5 μm, and dried and cured at room temperature. By doing so, the painted product (2
7) was obtained. <Example 28> In Example 27, except that a pigment (white pigment manufactured by Ishihara Sangyo Co., Ltd.) was added to the primer composition in an amount of 45 parts based on 100 parts of the total resin solid content in the total amount of the primer composition. Coated product (28) as in Example 27
I got <Comparative Example 6> A comparative inorganic paint (6) was obtained in the same manner as in Example 19, except that the addition amount of the titanium oxide powder used as the curing accelerator was changed to 1 part.

The comparative inorganic coating material (6) was applied to a glass substrate washed with acetone by a spray coating method, and the coating film was dried and cured at room temperature to obtain a comparative coated product (6). In addition, the thickness of the cured film is 0.5 μm.
Met. <Comparative Example 7> A comparative inorganic coating material (7) was obtained in the same manner as in Example 19, except that the addition amount of the titanium oxide powder used as the curing accelerator was changed to 85 parts.

The comparative inorganic coating material (7) was applied to a glass substrate washed with acetone by a spray coating method, and the coating film was dried and cured at room temperature to obtain a comparative coated product (7). In addition, the thickness of the cured film is 0.5 μm.
Met. <Comparative Example 8> The inorganic paint (22) obtained in Example 22 was applied to a glass substrate washed with acetone by a spin coating method, and the coating film was dried and cured at room temperature to obtain a comparative coated product (8). ) Got. The cured film had a thickness of 0.01 μm. <Comparative Example 9> The inorganic paint (23) obtained in Example 23 was applied to a glass substrate washed with acetone by a spray coating method, and the coating film was dried and cured at room temperature to obtain a comparative coated product (9). I got The film thickness after curing of the coating film is 20
μm. <Example 29> After thoroughly cleaning the hood of Toyota Sprinter (automobile; 1990 model) with acetone, the inorganic paint (18) obtained in Example 18 was cured by spray coating to obtain a cured coating film having a thickness of 0. It was applied to a thickness of 5 μm, and was dried and cured at room temperature for 24 hours to obtain a coated product (29). Example 30 A part (10 m ² ) of the south side of Matsushita Electric Works Co., Ltd. (building; Kadoma-shi, Osaka) was washed with hydrofluoric acid, and further sufficiently washed with acetone. Inorganic paint (18) is cured by spray coating.
μm, and dried and cured at about 20 ° C. under an outside air temperature all day and night to obtain a coated product (30). <Example 31> Lighting window (model M) manufactured by Matsushita Electric Works Co., Ltd.
WT2025JH), the inorganic coating (22) obtained in Example 22 was spray-coated to a cured coating thickness of 0.5 μm.
m and dried and cured at room temperature for 24 hours to obtain a coated product (31). <Example 32> A part of the entire glass (about 250 cm) of the draft in the intermediate laboratory on the site of Osaka Kadoma, Matsushita Electric Works, Ltd.
² ) The inorganic paint (22) obtained in Example 22 was applied by a spray coating method so as to have a cured film thickness of 0.5 μm, and dried and cured at room temperature for 24 hours to obtain a coated product (32). I got <Example 33> An inorganic paint (22) obtained in Example 22 was applied to a part of a road sign (approximately 1400 cm ² ) with a size of 600 mmφ and a height of 1200 mm on the site of Matsushita Electric Works Osaka Kadoma. By spray coating method
The coated product (33) was obtained by applying the solution to a thickness of μm and drying and curing it all day and night at room temperature. <Example 34> The inorganic paint (22) obtained in Example 22 was cured by a spray coating method on a window glass (1 m ² , 6 mm thick) of a building on the site of Osaka Kadoma, Matsushita Electric Works, Ltd. It was applied to a thickness of 1.0 μm, and was dried and cured at room temperature for 24 hours to obtain a coated product (34). <Example 35> The inorganic coating material obtained in Example 22 was applied to a part of the entire glass, poles, and fixtures of a road lighting fixture (model YA32020) installed at the front gate of Matsushita Electric Works, Ltd., Osaka Kadoma. 22) Spray coating method, cured film thickness 0.5μ
m and dried and cured at room temperature for 24 hours to obtain a coated product (35). <Example 36> Fuji-type fluorescent light fixture (model FA22) installed in the kitchen of an in-house cafeteria on the site of Matsushita Electric Works, Ltd. Osaka Kadoma
063), the inorganic paint (22) obtained in Example 22 was spray-coated on a part of the reflection plate to form a cured film having a thickness of 0.5 μm.
And dried and cured at room temperature for 24 hours to obtain a coated product (36). <Example 37> In Example 1, as a curing accelerator,
An inorganic paint (37) was obtained in the same manner as in Example 1, except that the same amount of strontium titanate (a reagent manufactured by Furuuchi Chemical Co., Ltd.) was used instead of the titanium oxide sol.

The inorganic coating (37) was applied to a glass substrate washed with acetone by a spray coating method, and the coating was dried and cured at room temperature to obtain a coated product (37). The cured film had a thickness of 0.5 μm. <Example 38> In Example 1, as a curing accelerator,
Instead of titanium oxide sol, a 1: 1 mixture by weight of titanium oxide (trade name “ST-01” manufactured by Ishihara Sangyo Co., Ltd.) and zinc oxide (trade name “reagent ZnO” manufactured by Nacalai Tesque, Inc.) Was used in the same manner as in Example 1 except that the same amount was used to obtain an inorganic paint (38).

The inorganic coating (38) was applied to a glass substrate washed with acetone by a spray coating method, and the coating was dried and cured at room temperature to obtain a coated product (38). The cured film had a thickness of 0.5 μm. <Comparative Example 10> A comparative inorganic paint (10) was obtained in the same manner as in Example 1 except that no curing accelerator was used.

This comparative inorganic paint (10) was applied to a glass substrate washed with acetone by a spray coating method.
The coating film was dried and cured at room temperature to obtain a comparative coated product (10). Incidentally, the film thickness after curing of the coating film is 0.5μ.
m. <Example 39> A coated product (39) was obtained in the same manner as in Example 1, except that the film thickness after curing of the coating film was changed to 9.5 µm. <Example 40> A coated product (40) was obtained in the same manner as in Example 23 except that the film thickness after curing of the coating film was changed to 9.5 µm. <Comparative Example 11> A comparative coated product (11) was obtained in the same manner as in Example 1, except that the film thickness after curing of the coating film was changed to 11 µm. <Comparative Example 12> A comparative coated product (12) was obtained in the same manner as in Example 23 except that the film thickness after curing of the coating film was changed to 11 µm.

The performance of the paints and coated articles obtained as described above was evaluated by the following methods. <Evaluation method> (Coating film performance): Evaluated by a boiling test described in JIS-K5400.

(Room temperature curing performance): Evaluated by the charging half-life described in JIS-L1094. In measuring the charging half-life, use a static meter manufactured by Nippon Staticc.
Using S4101, black light 10W for the sample
(0.6 mW / cm ² ) was measured after irradiation for 6 hours.

(Evaluation of a product coated on an article or the like): The evaluation was made based on the difference in stains between a coated portion and an unpainted portion after three months from coating. The results are shown in Tables 1 to 3.

[0115]

[Table 1]

[0116]

[Table 2]

[0117]

[Table 3]

In Examples 29 to 36, adhesion of dirt on the painted portion was hardly observed as compared with the unpainted portion.

[0119]

According to the low-temperature curing inorganic coating method of the present invention, a curing accelerator is added to the silicone resin to promote the curing, so that the curing time of the coating film is shortened, and the weather resistance of the coating film is reduced. Is also high, and it is hard to be damaged. This effect of accelerating hardening is particularly remarkable at room temperature as compared with the case where the above-mentioned conventional low-temperature-curable inorganic paint is used.

Since the coating used in the present invention is an inorganic coating, the coating performance is hardly impaired by the addition of a curing accelerator, is hardly deteriorated by ultraviolet rays, and is excellent in weather resistance, durability and the like. A cured film can be formed. Of course, it is also possible to adjust to various colors. The inorganic coating used in the present invention controls the antistatic property and other various functions, the curing performance, the coating film properties, etc. according to the application by changing the ratio of the resin and the curing accelerator contained therein. Can be.

The inorganic coating used in the present invention can be cured not only at room temperature but also under heat, so that it can be used in a wide range of drying and curing conditions or temperature. Therefore, not only can a substrate having a shape difficult to apply heat uniformly, a substrate having a large size or a substrate having poor heat resistance be coated, but also when performing a coating operation outdoors or the like. As described above, it can be applied even when it is difficult to apply heat or when a long time is not required for curing, so that its industrial value is high.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI B05D 7/14 B05D 7/14 L C08J 7/04 C08J 7/04 M C09D 5/00 C09D 5/00 D 7/12 7 / 12 Z 183/04 183/04

Claims (28)

[Claims] (1) In obtaining a coated product using an inorganic paint as a base material, the inorganic paint contains a silicone resin as a main component,
The curing accelerator contains 2 to 80 parts by weight based on a total of 100 parts by weight of the solid content in terms of the condensation compound of the paint and the curing accelerator, and is characterized in that the coating film is cured at a low temperature of 100 ° C. or less. Low temperature curing inorganic coating method. 2. The low-temperature curing inorganic coating method according to claim 1, wherein the silicone resin is a silicone resin containing the following component (A). Component (A): With respect to 100 parts by weight of the silicon compound represented by the general formula R ² Si (OR ¹ ) ₃ , the general formula Si (OR ¹ )
A silicon compound and / or colloidal silica 5-30000 parts represented by _4, the general formula R ^{₂ 2} Si (OR
¹ ) A hydrolyzable polycondensate of a hydrolyzable mixture containing 0 to 60 parts by weight of a silicon compound represented by ₂ (wherein R ¹ and R ^{2 each} represent a monovalent hydrocarbon group). The weight average molecular weight of the hydrolyzed polycondensate is 900 in terms of polystyrene.
An organosiloxane solution adjusted as described above. 3. The silicone resin comprises the following (B):
It contains the components (C) and (D), and in the component (B),
Contains 5 to 95% by weight of silica as a solid content, and
The low-temperature curing inorganic coating method according to claim 1 or 2, wherein at least 50 mol% of the hydrolyzable organosilane as a raw material of the component (B) is an organosilane having m = 1. Component (B): represented by the general formula R ³ _m SiX _4-m (I) (where 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 represents a hydrolyzable group.) In a colloidal silica dispersed in an organic solvent, water or a mixed solvent thereof, the hydrolyzable group ( X) A silica-dispersed oligomer solution of an organosilane, which is partially hydrolyzed under the condition of using 0.001 to 0.5 mol of water per mol equivalent. Component (C): represented by the average composition formula R ⁴ _a Si (OH) _b O _{(4-ab) / 2} ... (II) (where R ⁴ is the same or different and substituted or unsubstituted and has 1 to 1 carbon atoms) 8 represents a monovalent hydrocarbon group, wherein a and b are respectively 0.2 ≦ a ≦ 2, 0.0001 ≦ b ≦
3, a number satisfying the relationship of a + b <4. ), A solution of a polyorganosiloxane containing silanol groups in the molecule. Component (D): curing catalyst. 4. The hardening accelerator includes titanium oxide, zinc oxide, tin oxide, iron oxide, zirconium oxide, tungsten oxide, chromium oxide, molybdenum oxide, ruthenium oxide,
Germanium oxide, lead oxide, cadmium oxide, copper oxide,
4. An optical semiconductor comprising at least one metal oxide selected from the group consisting of vanadium oxide, niobium oxide, tantalum oxide, manganese oxide, cobalt oxide, rhodium oxide, nickel oxide and rhenium oxide.
The low-temperature curing inorganic coating method according to any one of the above. 5. The low-temperature curing inorganic coating method according to claim 1, wherein the curing accelerator is in the form of a powder or a sol. 6. The low-temperature curing inorganic coating method according to claim 5, wherein the curing accelerator is a sol having a pH of 7 or less. 7. The low-temperature curing inorganic coating method according to claim 1, wherein a metal is carried on the surface of the curing accelerator. 8. The metal supported on the surface of the curing accelerator is at least one selected from the group consisting of silver, copper, iron, nickel, zinc, platinum, gold, palladium, cadmium, cobalt, rhodium and ruthenium. The method of claim 7, wherein the method is a seed. 9. The method according to claim 1, wherein the inorganic paint is coated on the surface of the base material to a thickness of 0.1 mm.
The low-temperature curing inorganic coating method according to any one of claims 1 to 6, wherein the coating is performed at a thickness of from 0.05 to 10 m. 10. The substrate according to claim 1, wherein the substrate is an inorganic substrate, an organic substrate,
An inorganic-organic composite substrate, a single material of a coating 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 substrates,
The composite material according to any one of claims 1 to 9, wherein the composite material is selected from the group consisting of a composite material obtained by combining at least two of them and a laminated material obtained by laminating at least two of these. The low-temperature curing inorganic coating method described in 1. 11. The base material is made of metal, glass, hollow,
Ceramics, cement, concrete, wood, wood, plastic, inorganic fiber reinforced plastic, a coating base having at least one inorganic coating and / or at least one organic coating on any one of these substrates The material according to claim 10, wherein the material is selected from the group consisting of a single material, a composite material obtained by combining at least two of these materials, and a laminated material obtained by laminating at least two of these materials. Low-temperature curing inorganic coating method. 12. The low-temperature curing inorganic coating method according to claim 10, wherein the coating film on the surface of the coating substrate is a primer layer. 13. The low-temperature curing according to claim 1, wherein the coated article is a building-related member having a coating film having a thickness of 0.05 to 10 μm on at least a part of a substrate. Inorganic painting method. 14. The low-temperature curing inorganic coating method according to claim 13, wherein the substrate is glass. 15. The low-temperature curing device according to claim 1, wherein the coated product is a building gate provided with a coating film having a thickness of 0.05 to 10 μm on at least a part of a substrate. Inorganic painting method. 16. The low-temperature-curable inorganic coating according to claim 1, wherein the coated article is a pillar provided with a coating film having a thickness of 0.05 to 10 μm on at least a part of a substrate. Method. 17. The low-temperature curing according to claim 1, wherein the coated article is a building fence provided with a coating film having a thickness of 0.05 to 10 μm on at least a part of a substrate. Inorganic painting method. 18. The coated article according to claim 1, wherein the coated article is provided with a coating film having a thickness of 0.05 to 10 μm on at least a part of a substrate, and is a member to be used for a building fence. A low-temperature curing inorganic coating method as described in Crab. 19. The low-temperature-curable inorganic coating according to claim 1, wherein the coated article is a window provided with a coating having a thickness of 0.05 to 10 μm on at least a part of a substrate. Method. 20. The method of claim 19, wherein the window is a daylighting window. 21. The low-temperature-curable inorganic material according to claim 1, wherein the coated article is a window frame provided with a coating film having a thickness of 0.05 to 10 μm on at least a part of a substrate. Painting method. 22. The automobile, wherein the coated article is provided with a coating film having a thickness of 0.05 to 10 μm on at least a part of a substrate,
The low-temperature curing inorganic coating method according to claim 1. 23. The low-temperature-curable inorganic material according to claim 1, wherein the coated product is a mechanical device provided with a coating film having a thickness of 0.05 to 10 μm on at least a part of a substrate. Painting method. 24. The low-temperature curing device according to claim 1, wherein the coated article is a road peripheral member provided with a coating film having a thickness of 0.05 to 10 μm on at least a part of a substrate. Inorganic painting method. 25. The method according to claim 24, wherein the road peripheral member is a traffic sign. 26. The low-temperature-curable inorganic material according to claim 1, wherein the coated article is a traffic sign provided with a coating having a thickness of 0.05 to 10 μm on at least a part of a substrate. Painting method. 27. The low-temperature curing inorganic material according to claim 1, wherein the coated article is a lighting fixture having a coating film having a thickness of 0.05 to 10 μm on at least a part of a substrate. Painting method. 28. The coated article is used for a lighting fixture having a coating film having a thickness of 0.05 to 10 μm on at least a part of a substrate, and is selected from the group consisting of glass, resin, metal and ceramics. The low-temperature-curable inorganic coating method according to any one of claims 1 to 12, wherein the member is a member made of at least one kind of material obtained.