JPH0867835A - Antimicrobial inorganic coating - Google Patents

Abstract

PURPOSE: To obtain the subject composition having an antimicrobial performance for a long period, capable of being baked at high temperatures and not generating cracks on coating films because of having good flexibility by adding an antimicrobial agent to an inorganic coating having a specific composition. CONSTITUTION: This composition comprises (A) an inorganic coating containing (i) 20-200 pts.wt. of a silicon compound of the formula: Si(OR<1> )4 and/or colloidal silica, (ii) 100 pts.wt. of a silicon compound of the formula: R<2> Si(OR<1> )3 (R<1> , R<2> are each a univalent hydrocarbon), and (iii) 0-60 pts.wt. of a silicon compound of the formula: R<2> Si(OR<1> )2 and having a weight-average mol.wt. of >=900 (converted into polystyrene) and (B) an antimicrobial agent. The component B is preferably an elusion type antimicrobial performance-possessing component, e.g. either one of silver, copper and zinc, or either one of a quaternary ammonium salt, an organic halogen-containing compound, a chlorine-containing compound, and an iodine compound.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an antibacterial inorganic coating material.

[0002]

2. Description of the Related Art In an antibacterial organic paint containing an antibacterial agent in an organic resin, the resin deteriorates after long-term use, and especially when it is used outdoors, dirt adheres to the surface,
There is a drawback that the antibacterial performance of the coating film is likely to decrease due to deterioration due to ultraviolet rays. Therefore, there are known silicate-based, phosphate-based, and inorganic coatings containing an antibacterial agent in a zirconium-based inorganic composition. The inorganic coatings have better durability than organic coatings, but both are Since it needs to be baked at a high temperature of 200 ° C or higher, the usable range is limited, and it is not suitable for direct application to building materials and plastics. It should be noted that the silicate-based inorganic coating material has a drawback in that alkali is liable to be leached on the surface to easily cause a white bloom phenomenon after long-term use. Also,
Japanese Unexamined Patent Publication (Kokai) No. 62-57470 discloses an inorganic coating material containing a metal alkoxide. Although this inorganic coating material cures at 200 ° C. or lower, the coating film has no flexibility,
There is a problem that cracks easily occur. In recent years, because of the necessity of using paints for a wide variety of materials, there is a demand for paints that maintain antibacterial performance even when used for a long period of time, and that can be baked at a temperature of 200 ° C. or less without cracks.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned facts, and an object of the present invention is to maintain antibacterial performance for a long time, to be baked at a temperature of 200 ° C. or less, and to be flexible. An object is to provide an antibacterial inorganic paint having properties.

[0004]

The antibacterial inorganic paint according to claim 1 of the present invention is characterized in that the inorganic paint having the following composition contains an antibacterial agent. The above inorganic paint is
(A) A silicon compound represented by the general formula: Si (OR ¹ ) ₄ and / or colloidal silica of 20 to 200
Parts by weight, (b) 100 parts by weight of a silicon compound represented by the general formula: R ² Si (OR ¹ ) ₃ , and (c) silicon represented by the general formula: R ² ₂ Si (OR ¹ ) _2. Compound 0
The weight average molecular weight of the inorganic coating material containing the above components in an amount of -60 parts by weight and (d) 900 or more in terms of polystyrene. [The above R ¹ and R ² represent a monovalent hydrocarbon group. The antibacterial inorganic coating material according to claim 2 of the present invention is characterized in that the inorganic coating material having the following composition contains an antibacterial agent. The above-mentioned inorganic coating material comprises (i) 0.001 to 0.5 of water per 1 mol of X in mol of colloidal silica in which a hydrolyzable organosilane represented by the following general formula [1] is dispersed in an organic solvent or water. A silica-dispersed oligomer solution of organosilane partially hydrolyzed under the condition of using moles, and R ³ _n SiX _4-n [1] [wherein, R ³ is the same or different and is substituted or unsubstituted C 1 to C 1 8 is a monovalent hydrocarbon group, n is an integer of 0 to 3, and X is a hydrolyzable group. (B) A polyorganosiloxane having a silanol group in the molecule represented by the following formula [2], and R ⁴ _a Si (OH) _b O _{(4-ab) / 2} [2] [In the formula, R ⁴ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and a and b are 0.2 ≦ a ≦ 2 and 0.0001 ≦ b ≦, respectively. 3, a +
It is a number that satisfies the relationship of b <4. (C) a catalyst, and (D) the colloidal silica of the silica-dispersed oligomer solution has a silica content of 5 to 95% by weight.
At least 50 mol% of the hydrolyzable organosilane is an organosilane in which n in the formula [1] is 1, and (e) 1 to 1 of the above silica-dispersed oligomer solution.
9 parts by weight of 9 parts by weight of the above polyorganosiloxane
9 to 1 part by weight.

The antibacterial inorganic paint according to claim 3 of the present invention is the antibacterial inorganic paint according to claim 1 or 2, wherein the antibacterial agent contains a component having an elution type antibacterial performance. Characterize.

The antibacterial inorganic paint according to claim 4 of the present invention is the antibacterial inorganic paint according to claim 3, wherein the component having the elution-type antibacterial performance is silver, copper, zinc, nickel, palladium or platinum. And at least one selected from the group consisting of gold, cadmium, mercury, cobalt, and rhodium.

The antibacterial inorganic paint according to claim 5 of the present invention is the antibacterial inorganic paint according to any one of claims 1 to 4, wherein the antibacterial agent is a quaternary ammonium salt. To do.

The antibacterial inorganic paint according to claim 6 of the present invention is the antibacterial inorganic paint according to any one of claims 1 to 5, wherein the antibacterial agent is an organic halogen-containing compound, a chlorine-containing compound or an iodine compound. At least one of
It is characterized by containing a seed.

The antibacterial inorganic paint according to claim 7 of the present invention is the antibacterial inorganic paint according to any one of claims 1 to 6, characterized in that it contains a component having a photocatalytic function as the antibacterial agent. And

The antibacterial inorganic paint according to claim 8 of the present invention is the antibacterial inorganic paint according to claim 7, wherein the component having a photocatalytic function is 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, rhenium oxide It is characterized in that it is at least one kind.

The antibacterial inorganic paint according to claim 9 of the present invention is the antibacterial inorganic paint according to any one of claims 1 to 8, wherein an oxide having a photocatalytic function is inserted between the layers as the antibacterial agent. It is characterized by being a clay mineral.

The antibacterial inorganic paint according to claim 10 of the present invention is the antibacterial inorganic paint according to claim 9, wherein the oxide having a photocatalytic function is titanium oxide, zinc oxide, tin oxide, iron oxide, or oxide. From the group consisting of zirconium, 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 and rhenium oxide. It is characterized in that it is at least one selected.

An antibacterial inorganic paint according to claim 11 of the present invention is the antibacterial inorganic paint according to any one of claims 7 to 10, which has the photocatalytic function, or
The oxide is loaded with a metal.

The antibacterial inorganic paint according to claim 12 of the present invention is the antibacterial inorganic paint according to claim 11, wherein the metal is silver, copper, iron, nickel, zinc, platinum, gold, palladium, cadmium, It is at least one selected from the group consisting of cobalt, rhodium and ruthenium.

The present invention will be described in detail below. The antibacterial inorganic coating material of the present invention contains an antibacterial agent in the inorganic coating material.

The inorganic coating material will be described. The inorganic coating of the antibacterial inorganic coating according to claim 1 of the present invention is a silicon compound having a general formula represented by the following formula [3], and / or
20 to 200 parts by weight of colloidal silica, general formula: Si (OR ¹ ) ₄ [3] 100 parts by weight of a silicon compound represented by the following general formula [4], and general formula: R ² Si ( OR ¹ ) ₃ [4] A silicon compound represented by the following formula [5] is added in an amount of 0 to 60.
It is contained in a proportion of parts by weight. General formula: R ² ₂ Si (OR ¹ ) ₂ [5] In addition, the above R ¹ and R ² represent a monovalent hydrocarbon group.

The above silicon compound has the following general formula [6]:
It is what is represented. R² _nSi (OR¹)_4-n [6] [n = 0 to 3, indicating R¹, R²Is a monovalent hydrocarbon group
Show. ] R of the previous formula [6]¹, R²Is a monovalent hydrocarbon group
Without limitation, R ²As C1-8 substitution or
Represents an unsubstituted hydrocarbon group, such as a methyl group or ethyl group.
Group, propyl group, butyl group, pentyl group, hexyl group
Group, alkyl group such as heptyl group, octyl group, cyclopentyl group
Cycloalkyl groups such as ethyl and cyclohexyl groups, 2
-Ara such as phenylethyl group and 3-phenylpropyl group
Aryl group such as alkyl group, phenyl group and tolyl group, vinyl group
Group, alkenyl group such as allyl group, chloromethyl group, γ
-Chloropropyl group, 3,3,3-trifluoropropyl group, etc.
Halogen-substituted hydrocarbon group and γ-methacryloxy
Propyl group, γ-glycidoxypropyl group, 3,4-E
Poxycyclohexylethyl group, γ-mercaptopropy
And a substituted hydrocarbon group such as a rutile group. Above all synthetic
Because of its ease or availability, it has 1 to 4 carbon atoms.
A kill group and a phenyl group are preferred.

As R ¹ in the above formula [6], ^one having an alkyl group having 1 to 4 carbon atoms as a main raw material is used. In particular, n = 0
Examples of the tetraalkoxysilane include tetramethoxysilane and tetraethoxysilane. Examples of the organotrialkoxysilane with n = 1 include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane and phenyltrimethoxysilane. , Phenyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane and the like. Furthermore, n = 2
Examples of the diorganodialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane. Examples of the triorganoalkoxysilane with n = 3 include trimethylmethoxysilane. , Trimethylethoxysilane, trimethylisopropoxysilane, dimethylisobutylmethoxysilane and the like.

The above R ¹ and R ² are represented by the above formulas [3], [4],
In [5], the same hydrocarbon group may be present or may be different.

The above-mentioned inorganic coating is prepared by, for example, diluting a silicon compound represented by the above formulas [3], [4] and [5] with a solvent, adding water or a catalyst as a curing agent, and hydrolyzing the compound. Also, it is prepared by performing a polycondensation reaction. The weight average molecular weight (Mw) of these silicon compounds is calculated in terms of polystyrene. At the time of this preparation, the weight average molecular weight (Mw) of the inorganic coating material is adjusted to 900 or more in terms of polystyrene. When the weight average molecular weight (Mw) is less than 900 in terms of polystyrene, curing shrinkage becomes large during the polycondensation reaction, and cracks are likely to occur in the coating film of the baked inorganic coating material.

The above-mentioned inorganic coating material may be used in combination with the silicon compound represented by the above formula [3], or alternatively, may contain colloidal silica as a component. The colloidal silica is
It is a water-dispersible colloidal silica dispersed in water or an organic solvent-dispersible colloidal silica dispersed in a non-aqueous organic solvent such as alcohol. The colloidal silica contains 20 to 50% by weight of silica as a solid content.
In the preparation of the inorganic coating material, the water-dispersible colloidal silica can use water existing as a component other than the solid content as a curing agent. Further, the organic solvent-dispersible colloidal silica can be easily prepared by substituting water for the organic solvent. Examples of the organic solvent in which the colloidal silica is dispersed include lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol, and isobutanol, ethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether acetate. Ethylene glycol derivatives, diethylene glycol, diethylene glycol derivatives such as diethylene glycol monobutyl ether, and diacetone alcohol, and the like, and one or more of these may be used. Furthermore, in combination with a hydrophilic organic solvent, toluene, xylene, ethyl acetate, butyl acetate,
Methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime and the like can also be used. The amount of the colloidal silica blended is the weight including the dispersion medium.

Water is generally used as a curing agent when preparing an inorganic coating, and the amount of this water is preferably 45% or less, more preferably 25% or less in the inorganic coating.

The organic solvent used for producing the inorganic coating is, for example, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoacetate. Examples thereof include ethylene glycol derivatives such as ethyl ether, diethylene glycol, diethylene glycol derivatives such as diethylene glycol monobutyl ether, and diacetone alcohol. One or two of these may be mentioned.
More than one seed is used. Further, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, etc. can be used in combination with the hydrophilic organic solvent.

When preparing the above-mentioned inorganic paint, p of the inorganic paint is used.
It is desirable that H be 3.8 to 6. When the pH is in this range, the inorganic coating composition has good storage stability, and when it is out of this pH range, the period from the preparation period to the coating period is limited. The method of adjusting the pH is not limited, but for example, when the pH becomes less than 3.8 when the materials are mixed, it may be adjusted by adding a basic reagent such as ammonia, and the pH exceeds 6 In this case, it may be adjusted by adding an acidic reagent such as hydrochloric acid.
Further, depending on the pH, when the progress of the reaction is slow in the state where the molecular weight is small, it may be heated to accelerate the reaction,
The pH may be lowered with an acidic reagent to proceed the reaction, and then a basic reagent may be added to adjust the pH to a predetermined value.

Next, the inorganic coating material of the antibacterial inorganic coating material according to claim 2 of the present invention will be described. This inorganic coating material comprises a colloidal silica in which a hydrolyzable organosilane represented by the following general formula [1] is dispersed in an organic solvent or water,
A silica-dispersed oligomer solution of organosilane partially hydrolyzed under the condition of using 0.001 to 0.5 mol of water per 1 mol of X, and a general formula: R ³ _n SiX _4-n [1] ³ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, n represents an integer of 0 to 3, and X represents a hydrolyzable group. ] A polyorganosiloxane having a silanol group in the molecule whose average composition formula is represented by the following formula [2], and an average composition formula: R ⁴ _a Si (OH) _b O _{(4-ab) / 2} [2 [Wherein, R ⁴ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and a and b are 0.2 ≦ a ≦ 2 and 0.0001 ≦ b, respectively. ≦ 3, a +
It is a number that satisfies the relationship of b <4. ] It consists of a catalyst. Further, in the above inorganic coating material, the silica dispersion oligomer solution contains 5 to 95% by weight of silica as a solid content, and at least 50 mol% of the hydrolyzable organosilane is contained in the organosilane of formula [1] where n is 1. And 1 to 99 parts by weight of the silica dispersion oligomer solution,
It contains 99 to 1 part by weight of the above polyorganosiloxane.

The silica-dispersed oligomer of the above-mentioned silica-dispersed oligomer solution is the main component of the base polymer having a hydrolyzable group as a functional group involved in the curing reaction when forming a coating film. This silica-dispersed oligomer is an organic solvent,
Alternatively, the colloidal silica dispersed in water may be added to the above formula [1]
It is obtained by partially hydrolyzing the hydrolyzable organosilane with water in colloidal silica or water added separately, by adding one or more hydrolyzable organosilanes represented by

R ³ of the hydrolyzable organosilane represented by the above formula [1] is a substituted or unsubstituted 1 having 1 to 8 carbon atoms.
A valent hydrocarbon group is shown, and specifically, a hydrocarbon group similar to the above R ² is exemplified.

Examples of X representing the above hydrolyzable group include an alkoxy group, an acetoxy group, an oxime group, an enoxy group, an amino group, an aminoxy group and an amide group. Among these, the alkoxy group is preferable because it is easily available and the silica dispersion oligomer solution is easily prepared.

Such a hydrolyzable organosilane is
Monofunctional, di-, tri-, and tetra-functional alkoxysilanes, acetoxysilanes, oximesilanes, and enoxysilanes in which n in the chemical formula represented by the above formula [1] is an integer of 0 to 3 And aminosilanes, aminoxysilanes, amidosilanes and the like. Among these, alkoxysilanes are preferable because they are easily available and a silica dispersion oligomer solution is easily prepared. Examples of the tetraalkoxysilane with n = 0 include tetramethoxysilane and tetraethoxysilane,
Examples of the organotrialkoxysilane having n = 1 include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and 3,3,3-trifluoropropyltrimethoxysilane. Is exemplified. Further, as a diorganodialkoxysilane of n = 2,
Examples of dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, and the like are given. As triorganoalkoxysilane of n = 3,
Examples include trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, and dimethylisobutylmethoxysilane. Furthermore, an organosilane compound generally called a silane coupling agent is also included in the above alkoxysilanes.

It is necessary that at least 50 mol% of the above-mentioned hydrolyzable organosilane is a trifunctional organosilane represented by the formula [1] where n is 1. The proportion of the trifunctional organosilane is preferably 60 mol% or more, more preferably 70 mol% or more. If this content is less than 50 mol%, sufficient coating film hardness cannot be obtained, and the dry curability tends to be poor.

The colloidal silica in which the above hydrolyzable organosilane is dispersed in an organic solvent or water enhances the hardness of the cured coating film of the inorganic coating material. Examples of the colloidal silica include the water-dispersible colloidal silica and the organic solvent-dispersible colloidal silica described in the inorganic coating material according to claim 1.

The colloidal silica contains silica in the range of 5 to 95% by weight as a solid content. This content is 1
0 to 90% by weight is preferable, more preferably 20 to 85
% By weight. When the content is less than 5% by weight, the hardness of the coating film of the inorganic coating cannot be obtained, and when the content exceeds 95% by weight, it becomes difficult to uniformly disperse silica, and problems such as easy gelation occur. Cheap.

The hydrolyzable organosilane represented by the above formula [1] is partially hydrolyzed in an organic solvent or colloidal silica dispersed in water to obtain a silica-dispersed oligomer solution of organosilane. The amount of water relative to the hydrolyzable organosilane was 0.
001 to 0.5 mol is preferable. If the amount of water is less than 0.001 mol, sufficient partial hydrolysis cannot be obtained, and if it exceeds 0.5 mol, the stability of the partial hydrolyzate becomes poor. The method of partial hydrolysis is not particularly limited, and it is sufficient to mix the hydrolyzable organosilane and colloidal silica and add predetermined water, at which time the partial hydrolysis reaction proceeds at room temperature. In addition, you may heat at 60-100 degreeC in order to accelerate | stimulate the said partial hydrolysis reaction. Further, for the purpose of promoting partial hydrolysis reaction, hydrochloric acid, acetic acid, halogenated silane, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, Organic and inorganic acids such as toluene sulfonic acid and oxalic acid may be used as catalysts.

In order to obtain stable performance of the silica-dispersed oligomer solution for a long period of time, the pH of the solution is set to 2.0 to 7.0,
The pH is preferably 2.5 to 6.5, more preferably the pH.
Is preferably 3.0 to 6.0. When the pH is out of this range, particularly when the amount of water is 0.3 mol or more relative to 1 mol of the hydrolyzable group (X), the long-term performance deterioration of the silica-dispersed oligomer solution is remarkable. The method of adjusting the pH is not limited, but when the pH of the liquid deviates from the above range to the acidic side, it may be adjusted by adding a basic reagent such as ammonia or ethylenediamine. When the pH deviates to the basic side, hydrochloric acid is added. ,
It may be adjusted by adding an acidic reagent such as nitric acid or acetic acid.

The silanol group-containing polyorganosiloxane of the above-mentioned inorganic paint has an average compositional formula represented by the above formula [2].

R ⁴ in the above formula [2] represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and specific examples thereof include the same hydrocarbon group as R ² described above. However, preferably, an alkyl group having 1 to 4 carbon atoms, phenyl group, vinyl group, γ-glycidoxypropyl group, γ-methacryloxypropyl group, γ-aminopropyl group, 3,3,3-trifluoro group It is a substituted hydrocarbon group such as a propyl group, more preferably a methyl group and a phenyl group. Further, a and b in the formula [2] are 0.2 ≦ a ≦ 2 and 0.0001, respectively.
It is a number that satisfies the relationship of ≦ b ≦ 3 and a + b <4. If a is less than 0.2 or b is more than 3, there is an inconvenience such as cracking in the cured coating film, and if a is more than 2.0 and less than 4 or b is less than 0.0001, curing proceeds well. do not do.

As the polyorganosiloxane containing a silanol group, methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, or one or a mixture of two or more alkoxysilanes corresponding thereto is known. It can be obtained by hydrolysis with a large amount of water according to the method.
In order to obtain the polyorganosiloxane containing the silanol group, when hydrolyzed with an alkoxysilane,
A small amount of unhydrolyzed alkoxy groups may remain. That is, a polyorganosiloxane in which a silanol group and an extremely small amount of an alkoxy group coexist may be obtained, but such a polyorganosiloxane may be used.

The above catalyst accelerates the condensation reaction between the above-mentioned silica-dispersed oligomer solution and polyorganosiloxane,
It cures the coating film. Examples of the catalyst include alkyl titanates, tin octylate and diptyltin dilaurate, metal salts of carboxylic acids such as dioctyltin dimaleate, dibutylamine-2-hexoate, dimethylamine acetate, amine salts such as ethanolamine acetate, Carboxylic acid quaternary ammonium salts such as tetramethylammonium acetate, amines such as tetraethylpentamine, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxy Amine-based silane coupling agents such as silanes, acids such as p-toluenesulfonic acid, phthalic acid and hydrochloric acid, aluminum compounds such as aluminum alkoxides and aluminum chelates, alkali catalysts such as sodium hydroxide, tetraisopropyl titanate , Tetrabutyl titanate, titanium compounds such as titanium tetraacetyl acetonate, methyltrichlorosilane, dimethyldichlorosilane, halogenated silane such as trimethyl monochloro silane, and the like.

The silica dispersion oligomer solution and the polyorganosiloxane are compounded in a proportion of 1 to 99 parts by weight of the silica dispersion oligomer solution and 99 to 1 parts by weight of the polyorganosiloxane, preferably the silica. The dispersion oligomer solution is 5 to 95 parts by weight, and the polyorganosiloxane is 95 to 5 parts by weight, and more preferably, the silica dispersion oligomer solution is 10 to 9 parts by weight.
90 to 90 parts by weight of the above polyorganosiloxane
10 parts by weight. If the proportion of the silica-dispersed oligomer solution is less than the above range, it is difficult to cure at room temperature, and sufficient hardness of the coating film cannot be obtained. If the ratio of the silica-dispersed oligomer solution is more than the above range, the curability becomes unstable.

The content of the catalyst is preferably 0.0001 to 10 parts by weight based on 100 parts by weight of the total amount of the silica-dispersed oligomer solution and the polyorganosiloxane. It is more preferably 0.0005 to 8 parts by weight, and most preferably 0.0007 to 5 parts by weight. 0.00 catalyst
If it is less than 01 parts by weight, it will not cure at room temperature, and if it exceeds 10 parts by weight, heat resistance and weather resistance will be poor.

The hydrolyzable group contained in the silica-dispersed oligomer and the silanol group in the polyorganosiloxane are subjected to a condensation reaction in the presence of a catalyst at room temperature or at a low temperature of 200 ° C. or lower to form a coating film. To do. Therefore, the inorganic coating material is cured at room temperature with little influence of humidity. Further, the condensation reaction can be promoted by the above-mentioned low temperature heating.

The above-mentioned inorganic paint can be diluted with various organic solvents for easy handling. The type of the organic solvent is appropriately selected depending on the types and molecular weights of the monovalent hydrocarbon groups in the silica-dispersed oligomer solution and the polyorganosiloxane. Examples of the organic solvent include the same organic solvents as described in the inorganic coating composition according to claim 1.

Next, the antibacterial agent contained in the antibacterial inorganic coating material of the present invention will be described. As the above-mentioned antibacterial agent, various antibacterial agents such as one containing a component having an elution type antibacterial property and one containing a component having a photocatalytic function are appropriately selected. Examples of the component having an elution type antibacterial property contained in the above antibacterial agent include silver, copper, zinc, nickel, palladium, platinum, gold, cadmium, mercury, cobalt, rhodium and the like. Furthermore, as an antibacterial agent,
For example, quaternary ammonium salts, organic halogen-containing compounds, chlorine-containing compounds, iodine compounds and the like can be mentioned. These inorganic paints contain these alone or in combination of two or more. Further, the above component is zeolite or activated alumina,
It may be dispersed in a porous material such as silica gel and supported, provided that it does not impair the function and weather resistance of the inorganic coating material.

Examples of the component having a photocatalytic function contained in the above antibacterial agent include titanium oxide, zinc oxide, tin oxide, iron oxide, zirconium oxide, tungsten oxide, chromium oxide, molybdenum oxide, ruthenium oxide, germanium oxide, and oxide. Examples thereof include lead, cadmium oxide, copper oxide, vanadium oxide, niobium oxide, tantalum oxide, manganese oxide, cobalt oxide, rhodium oxide, rhenium oxide, and one of these or a mixture of two or more thereof. The above-mentioned component having a photocatalytic function is mixed in the inorganic coating within a range that does not impair the function and weather resistance of the inorganic coating.

Further, the antibacterial inorganic coating material may contain an antibacterial agent in a state where a metal is supported on the component having the photocatalytic function. Examples of the metal include silver, copper, iron, nickel, zinc, platinum, gold, palladium, cadmium, cobalt, rhodium, and ruthenium, or a mixture of two or more thereof. When a metal is supported on a component having a photocatalytic function, charge separation is promoted and the catalyst of the photocatalyst is activated, so that the antibacterial property is improved, which is preferable. It is preferable that the carried metal has antibacterial properties because the antibacterial properties are further improved.

Further, the antibacterial inorganic coating material may contain, as an antibacterial agent, a clay mineral in which an oxide having a photocatalytic function is inserted between layers. As the clay mineral, a smectite type mineral having swelling property is suitable. The smectite-type mineral may be either natural or synthetic. The oxide to be inserted in the clay mineral is 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, One or more of vanadium oxide, niobium oxide, tantalum oxide, manganese oxide, cobalt oxide, rhodium oxide, rhenium oxide and the like can be mentioned. When an oxide is inserted between layers of clay minerals, the oxide is retained by the fine particles, exhibits high photocatalytic activity, and improves antibacterial properties. Further, a metal may be supported on the oxide having a photocatalytic function inserted between the layers. As the above metal,
Examples thereof include silver, copper, iron, nickel, zinc, platinum, gold, palladium, cadmium, cobalt, rhodium and ruthenium, or a mixture of two or more thereof. When a metal is supported on an oxide having a photocatalytic function, charge separation is promoted and the catalyst of the photocatalyst is activated, so that the antibacterial property is improved, which is preferable. It is preferable that the carried metal has antibacterial properties because the antibacterial properties are further improved.

In the case of producing an antibacterial inorganic coating material, the antibacterial agent containing the photocatalytic function and the oxide is used as the antibacterial agent containing the photocatalytic function and the oxide or the oxide dispersed in a solvent. Used in. The above powder is obtained by drying such as heat drying, freeze drying and supercritical drying.

The antibacterial inorganic paint is applied by brushing,
Various coating methods such as spray coating, dipping, curtain and knife coating can be adopted. At the time of coating, it may be appropriately diluted with an organic solvent, if necessary.

As a method for treating a coating film coated with an antibacterial inorganic coating, depending on the type and content of the above-mentioned antibacterial agent, the silicone component in the inorganic coating wraps the antibacterial agent component when the coating film is applied, and Since the properties may not be sufficiently exhibited, it is preferable to treat the surface of the coated and dried coating film with acid or alkali. When the surface of the coating film is treated with acid or alkali, the silicone component is eluted and the antibacterial agent is exposed on the surface, so that the antibacterial property is improved. The types of the acids and alkalis and the states of liquids and gases are not particularly limited, but in the case of weak acids and weak alkalis, it is necessary to take a long treatment time. As the treatment method, the treatment may be performed by dipping in a solution or by putting an object to be coated in a chamber and treating in a gas phase.

[0050]

EXAMPLES Next, examples of the present invention and comparative examples will be described. The molecular weight is a value determined by gel permeation chromatography (GPC) using a measurement model HLC8020 (manufactured by Tosoh Corporation) and obtained from a calibration curve of standard polystyrene.

Example 1 Tetraethoxysilane was used as the silicon compound represented by the above formula [3], and IPA organosilica sol was used as the colloidal silica (Catalyst Kasei: trade name OSCAL14).
32), methyltrimethoxysilane was used as the silicon compound represented by the formula [4], dimethyldimethoxysilane was used as the silicon compound represented by the formula [5], and silver nitrate was used as the antibacterial agent.

To 100 parts by weight of methyltrimethoxysilane (hereinafter referred to as "part"), 10 parts of tetraethoxysilane,
90 parts of IPA organosilica sol, 30 parts of dimethyldimethoxysilane, isopropyl alcohol (IPA)
90 parts of water was added and the mixture was stirred. This was adjusted to a weight average molecular weight (hereinafter referred to as Mw) of 1500 in a constant temperature bath at 60 ° C. 20 parts of silver nitrate was added to this prepared liquid to obtain an antibacterial inorganic coating material.

The obtained antibacterial inorganic coating material was applied to an alumina substrate washed with acetone and dried at a temperature of 150 ° C. for 1 hour. The film thickness of the coating film after curing was 10 μm.

Example 2 An antibacterial inorganic coating material was obtained in the same manner as in Example 1 except that zinc nitrate was used as the antibacterial agent instead of the silver nitrate of Example 1. The obtained antibacterial inorganic coating material was applied to an alumina substrate washed with acetone in the same manner as in Example 1 and dried at a temperature of 150 ° C for 1 hour. The film thickness of the coating film after curing was 10 μm.

Example 3 An antibacterial inorganic coating material was obtained in the same manner as in Example 1 except that octadecyltrimethylamine (manufactured by NOF CORPORATION) (trade name: Cation AB) was used as the antibacterial agent in place of the silver nitrate of Example 1. It was The obtained antibacterial inorganic coating material was applied to an alumina substrate washed with acetone in the same manner as in Example 1, and the temperature was set to 15
It was dried at 0 ° C. for 1 hour. The thickness of the coating film after curing is 10 μm
Met.

Example 4 The same as Example 1 except that 20 parts of silver nitrate of Example 1 was replaced with 10 parts of an organic iodine compound (Takeda Yakuhin Kogyo Co., Ltd .: trade name Courtside 123) as an antibacterial agent. Then, an antibacterial inorganic coating material was obtained. The obtained antibacterial inorganic paint,
It was coated on an alumina substrate washed with acetone in the same manner as in Example 1 and dried at a temperature of 150 ° C. for 1 hour. The film thickness of the coating film after curing was 10 μm.

Example 5 IPA organosilica sol (Catalyst Kasei Co., Ltd .: trade name OSCAL1432) as colloidal silica, methyltrimethoxysilane as a silicon compound represented by the above formula [4], and a benzimidazole compound as an antibacterial agent. A compounding agent of an organic nitrogen halogen compound (manufactured by Takeda Chemical Industries, Ltd .: trade name Courtside DX) was used.

To 100 parts of methyltrimethoxysilane, I
After mixing 60 parts of PA organosilica sol and 100 parts of isopropyl alcohol (IPA), 60 parts of water was added and stirred. The molecular weight of this was adjusted to Mw = 950 in a 60 ° C. thermostat. 5 parts of a compounding agent of a benzimidazole compound and an organic nitrogen halogen compound was added to this prepared liquid to obtain an antibacterial inorganic coating material.

The obtained antibacterial inorganic coating material was applied to an alumina substrate washed with acetone and dried at a temperature of 150 ° C. for 1 hour. The film thickness of the coating film after curing was 10 μm.

Example 6 The antibacterial properties were the same as in Example 5 except that 20 parts of titanium oxide powder (manufactured by Nippon Aerosil Co., Ltd .: trade name P-25) was used instead of 5 parts of the antibacterial agent of Example 5. An inorganic paint was obtained.
The obtained antibacterial inorganic coating material was applied to an alumina substrate washed with acetone in the same manner as in Example 1 and dried at a temperature of 150 ° C for 1 hour. The film thickness of the coating film after curing was 10 μm.

Example 7 As an antibacterial agent, a titanium oxide powder carrying silver was prepared as follows. Titanium oxide powder (manufactured by Nippon Aerosil Co., Ltd .: trade name P-25) was dispersed in water so as to be an aqueous solution of 1% by weight (hereinafter referred to as%), and then the ratio of silver was 5% with respect to the titanium oxide powder. Add silver nitrate so that
It was irradiated with ultraviolet rays for 3 hours to support silver on the surface of titanium oxide. Then, it dried and the titanium oxide powder carrying silver was obtained. Methyltrimethoxysilane 1 as in Example 5
After mixing 60 parts of IPA organosilica sol and 100 parts of isopropyl alcohol (IPA) with 00 parts,
60 parts of water was added and stirred, and the molecular weight was adjusted to Mw = 950 in a constant temperature bath at 60 ° C. 20 parts of the above titanium oxide powder supporting silver was added to the prepared liquid to obtain an antibacterial inorganic coating material. The obtained antibacterial inorganic coating material was applied to an alumina substrate washed with acetone and dried at a temperature of 150 ° C for 1 hour. The film thickness of the coating film after curing was 10 μm.

Example 8 An antibacterial agent was prepared as follows. Titanium tetraisopropoxide was peptized with hydrochloric acid. 2N hydrochloric acid: tetraisopropoxide titanate = 10: 1 (weight) was used in the compounding ratio. Clay mineral N prepared by previously dispersing this reaction solution in water
a Montmorillonite (Kunimine Industries Co., Ltd .: trade name Kunipia F) was added to a 1% aqueous solution, and titania was inserted between the clay layers. (Hereinafter, titania is inserted between the clay layers will be referred to as PILC.) The composition ratio of this PILC was such that clay: titania = 1: 0.6 by weight. This PI
The LC was brought into contact with carbon dioxide in a supercritical state, the solvent was extracted and removed, and a dry powder of PILC was obtained.

In the same manner as in Example 5, 100 parts of methyltrimethoxysilane and 60 parts of IPA organosilica sol,
After mixing 100 parts of isopropyl alcohol (IPA), 60 parts of water was added and stirred, and the molecular weight was adjusted to Mw = 950 in a constant temperature bath at 60 ° C. In this prepared liquid,
20 parts of the dry powder of PILC was added to obtain an antibacterial inorganic coating material. The obtained antibacterial inorganic coating material was applied to an alumina substrate washed with acetone and dried at a temperature of 150 ° C for 1 hour. The film thickness of the coating film after curing was 10 μm.

Example 9 An antibacterial agent was prepared as follows. Titanium tetraisopropoxide was peptized with hydrochloric acid. 2N hydrochloric acid: tetraisopropoxide titanate = 10: 1 (weight) was used in the compounding ratio. Clay mineral N prepared by previously dispersing this reaction solution in water
a Montmorillonite (Kunimine Industries Co., Ltd .: trade name Kunipia F) was added to a 1% aqueous solution, and titania was inserted between the clay layers. (Hereinafter, titania is inserted between the clay layers will be referred to as PILC.) The composition ratio of this PILC was such that clay: titania = 1: 0.6 by weight. This PI
A silver nitrate solution was added to the LC solution so that the silver content was 5% with respect to titania, and the solution was irradiated with ultraviolet rays for 3 hours to support silver on the titania surface. Then, it was contacted with carbon dioxide in a supercritical state, the solvent was extracted and removed, and a dry powder of PILC carrying silver was obtained.

In the same manner as in Example 5, 100 parts of methyltrimethoxysilane, 60 parts of IPA organosilica sol,
After mixing 100 parts of isopropyl alcohol (IPA), 60 parts of water was added and stirred, and the molecular weight was adjusted to Mw = 950 in a constant temperature bath at 60 ° C. In this prepared liquid,
20 parts of the dry powder of PILC carrying silver was added,
An antibacterial inorganic paint was obtained. The obtained antibacterial inorganic paint was applied to an alumina substrate washed with acetone, and the temperature was 150 ° C for 1 hour.
Dried for hours. The film thickness of the coating film after curing was 10 μm.

Next, (A-1 solution) and (A-2 solution) were prepared as silica-dispersed oligomer solutions, and (B-1 solution) and (B-2 solution) were prepared as polyorganosiloxane.

(A-1 liquid) Isopropanol-dispersed colloidal silica sol IPA-ST was placed in a flask equipped with a stirrer, a heating jacket, a condenser, and a thermometer.
(Particle size 10 to 20 mμ, solid content 30%, manufactured by Nissan Chemical Industries, Ltd.) 100 parts, methyltrimethoxysilane 68 parts, and water 10.8 parts were added and stirred at 65 ° C. for 5 hours. Partially hydrolyzed and cooled. Then, the solid content was 36% when left at room temperature for 48 hours. Hereinafter, this silica-dispersed oligomer solution is referred to as (A-1 liquid).

The number of moles of water relative to 1 mole of the hydrolyzable group was 0.4 mole, the content of silica in (A-1 solution) was 47.3%, and the amount of hydrolysis of n = 1 was 1. The mol% of the decomposable group-containing organosilane was 100 mol%.

(Liquid A-2) Isopropyl alcohol-dispersed colloidal silica sol IPA-in a flask equipped with a stirrer, heating jacket, condenser, and thermometer.
ST (particle size 10 to 20 mμ, solid content 30%, water 0.5
%, Manufactured by Nissan Chemical Industries, Ltd.), 68 parts of methyltrimethoxysilane, 18 parts of dimethyldimethoxysilane, 2.7 parts of water, 0.1 parts of acetic anhydride, and 80 ° C. with stirring. Partially hydrolyzed for 3 hours and cooled. Then, the solid content was 36% when left at room temperature for 48 hours. Hereinafter, this silica-dispersed oligomer solution is referred to as (A-2 liquid).

The number of moles of water relative to 1 mol of the hydrolyzable group was 0.1 mol, the content of silica in (A-2 solution) was 40.2%, and n = 1. The mol% of the decomposable group-containing organosilane was 77 mol%.

(Liquid B-1) A mixed liquid of 220 parts (1 mol) of methyltriisopropoxysilane and 150 parts of toluene was prepared. Next, the above mixed solution was put into a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel and a thermometer, and 108 parts of a 1% hydrochloric acid aqueous solution was added dropwise thereto over 20 minutes to obtain methyltriisopropoxysilane. It was hydrolyzed. After 40 minutes from the dropping, stirring was stopped and the mixture was allowed to stand to separate into two layers. Of this layer, the lower layer mixed solution of water and isopropyl alcohol containing a small amount of hydrochloric acid was separated and removed, and then the remaining toluene resin solution was washed with water to remove hydrochloric acid, and toluene was further removed under reduced pressure. By diluting the component with isopropyl alcohol, a 40% isopropyl alcohol solution of polyorganosiloxane containing silanol groups and having an average molecular weight of about 2000 was obtained. Less than,
This solution is referred to as (B-1 solution).

(Liquid B-2) 1000 parts of water and 50 parts of acetone were put into a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel and a thermometer, and 44.8 parts of methyltrichlorosilane (0. 3 mol), 38.7 parts (0.3 mol) of dimethyldichlorosilane, and 84.6 parts (0.4 mol) of phenyltrichlorosilane dissolved in 200 parts of toluene were added dropwise with stirring to be hydrolyzed. . After 40 minutes from the dropping, stirring was stopped, and the reaction solution was transferred to a separatory funnel and left standing to separate into two layers. Of this layer, the lower layer of hydrochloric acid water was separated and removed, and then the remaining toluene solution of polyorganosiloxane was removed by vacuum stripping to remove the remaining water and hydrochloric acid together with toluene to obtain an average molecular weight of about 3,000. A 60% toluene solution of the polyorganosiloxane containing silanol groups was obtained. Hereinafter, this solution is referred to as (B-2 solution).

Example 10 50 parts of the prepared liquid A-1 and 50 parts of the liquid B-2 were mixed with 2 parts of N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane as a catalyst, and then as an antibacterial agent. 20 parts of silver nitrate was added to obtain an antibacterial inorganic coating. The obtained antibacterial inorganic coating material was applied to an alumina substrate washed with acetone and dried at a temperature of 150 ° C for 1 hour. The film thickness of the coating film after curing was 10 μm.

Example 11 An antibacterial inorganic coating material was obtained in the same manner as in Example 10 except that zinc nitrate was used as the antibacterial agent instead of the silver nitrate of Example 10. The obtained antibacterial inorganic coating material was applied to an alumina substrate washed with acetone in the same manner as in Example 10 and dried at a temperature of 150 ° C for 1 hour. The film thickness of the coating film after curing was 10 μm.

Example 12 An antibacterial inorganic coating material was obtained in the same manner as in Example 10, except that octadecyltrimethylamine (manufactured by NOF CORPORATION) (trade name: Cation AB) was used as the antibacterial agent instead of the silver nitrate of Example 10. It was The obtained antibacterial inorganic paint was used in Example 10
In the same manner as above, it was applied to an alumina substrate washed with acetone and dried at a temperature of 150 ° C. for 1 hour. The film thickness of the coating after curing is 1
It was 0 μm.

Example 13 The same as Example 10 except that 20 parts of silver nitrate of Example 10 was replaced with 10 parts of an organic iodine compound (Takeda Yakuhin Kogyo Co., Ltd .: trade name Courtside 123) as an antibacterial agent. Then, an antibacterial inorganic coating material was obtained. The obtained antibacterial inorganic coating material was applied to an alumina substrate washed with acetone in the same manner as in Example 10 and dried at a temperature of 150 ° C for 1 hour. The film thickness of the coating film after curing was 10 μm.

Example 14 In place of 20 parts of silver nitrate of Example 10, 5 parts of a compounding agent (trade name: Courtside DX, manufactured by Takeda Pharmaceutical Co., Ltd.) of a benzimidazole compound and an organic nitrogen halogen compound as an antibacterial agent was used. An antibacterial inorganic coating material was obtained in the same manner as in Example 10 except that it was used. The obtained antibacterial inorganic paint was used in Example 10
In the same manner as above, it was applied to an alumina substrate washed with acetone and dried at a temperature of 150 ° C. for 1 hour. The film thickness of the coating after curing is 1
It was 0 μm.

Example 15 50 parts of the prepared solution A-2, 50 parts of the solution B-1 and 2 parts of N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane as a catalyst were mixed and then used as an antibacterial agent. Titanium oxide powder (Nippon Aerosil Co., Ltd .: trade name P-
20 parts of 25) was added to obtain an antibacterial inorganic coating material. The obtained antibacterial inorganic coating material was applied to an alumina substrate washed with acetone and dried at a temperature of 150 ° C for 1 hour. The film thickness of the coating film after curing was 10 μm.

Example 16 As an antibacterial agent, a titanium oxide powder carrying silver was prepared as follows. Titanium oxide powder (manufactured by Nippon Aerosil Co., Ltd .: trade name P-25) was dispersed in water so as to be an aqueous solution of 1% by weight (hereinafter referred to as%), and then the ratio of silver was 5% with respect to the titanium oxide powder. Add silver nitrate so that
It was irradiated with ultraviolet rays for 3 hours to support silver on the surface of titanium oxide. Then, it dried and the titanium oxide powder carrying silver was obtained.

As in Example 15, after mixing 50 parts of the prepared solution A-2, 50 parts of the solution B-1 and 2 parts of N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane as a catalyst, Then, 20 parts of the above titanium oxide powder was added to obtain an antibacterial inorganic coating material. The obtained antibacterial inorganic coating is applied to an alumina substrate washed with acetone, and the temperature is 150 ° C.
And dried for 1 hour. The film thickness of the coating film after curing was 10 μm.

Example 17 An antibacterial agent was prepared as follows. Titanium tetraisopropoxide was peptized with hydrochloric acid. 2N hydrochloric acid: tetraisopropoxide titanate = 10: 1 (weight) was used in the compounding ratio. Clay mineral N prepared by previously dispersing this reaction solution in water
a Montmorillonite (Kunimine Industries Co., Ltd .: trade name Kunipia F) was added to a 1% aqueous solution, and titania was inserted between the clay layers. (Hereinafter, titania is inserted between the clay layers will be referred to as PILC.) The composition ratio of this PILC was such that clay: titania = 1: 0.6 by weight. This PI
The LC was brought into contact with carbon dioxide in a supercritical state, the solvent was extracted and removed, and a dry powder of PILC was obtained.

As in Example 15, after mixing 50 parts of the prepared solution A-2, 50 parts of the solution B-1 and 2 parts of N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane as a catalyst, Then, 20 parts of the above dry powder of PILC was added to obtain an antibacterial inorganic coating material. The obtained antibacterial inorganic paint,
Apply to an alumina substrate washed with acetone at a temperature of 150
It was dried at ° C for 1 hour. The film thickness of the coating film after curing was 10 μm.

Example 18 An antibacterial agent was prepared as follows. Titanium tetraisopropoxide was peptized with hydrochloric acid. 2N hydrochloric acid: tetraisopropoxide titanate = 10: 1 (weight) was used in the compounding ratio. Clay mineral N prepared by previously dispersing this reaction solution in water
a Montmorillonite (Kunimine Industries Co., Ltd .: trade name Kunipia F) was added to a 1% aqueous solution, and titania was inserted between the clay layers. (Hereinafter, titania is inserted between the clay layers will be referred to as PILC.) The composition ratio of this PILC was such that clay: titania = 1: 0.6 by weight. This PI
A silver nitrate solution was added to the LC solution so that the silver content was 5% with respect to titania, and the solution was irradiated with ultraviolet rays for 3 hours to support silver on the titania surface. Then, it was contacted with carbon dioxide in a supercritical state, the solvent was extracted and removed, and a dry powder of PILC carrying silver was obtained.

As in Example 15, after mixing 50 parts of the prepared solution A-2, 50 parts of the solution B-1 and 2 parts of N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane as a catalyst, Then, 20 parts of the above dry powder of PILC carrying silver was added to obtain an antibacterial inorganic coating material. The obtained antibacterial inorganic coating material was applied to an alumina substrate washed with acetone and dried at a temperature of 150 ° C for 1 hour. The film thickness of the coating film after curing was 10 μm.

Comparative Example 1 100 parts of methyltrimethoxysilane, 10 parts of tetraethoxysilane, 90 parts of IPA organosilica sol,
After mixing 30 parts of dimethyldimethoxysilane and 100 parts of isopropyl alcohol (IPA), 90 parts of water was added and stirred. This was adjusted to a weight average molecular weight (hereinafter referred to as Mw) of 1500 in a constant temperature bath of 60 ° C. to obtain an inorganic coating material. The obtained inorganic coating material was applied to an alumina substrate washed with acetone and dried at a temperature of 150 ° C for 1 hour. The film thickness of the coating film after curing was 10 μm.

Comparative Example 2 50 parts of the prepared solution A-1 and 50 parts of solution B-2 were mixed with 2 parts of N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane as a catalyst to obtain an inorganic coating material. . Apply the obtained inorganic paint to an alumina substrate washed with acetone,
It was dried at a temperature of 150 ° C. for 1 hour. The film thickness of the coating film after curing was 10 μm.

The antibacterial properties of the coating films applied to the alumina substrates of Examples 1 to 18 and Comparative Examples 1 and 2 were evaluated.
For the evaluation, a solution containing a certain number of bacteria was dropped onto the coated alumina substrate by the drop method, and changes in the number of bacteria at the initial stage and after 6 hours were measured. E. coli was used as the bacterium, and the measurement was 350
It was performed under an illuminance of 0 lux. The results are shown in Table 1, and the antibacterial effect was good in all Examples. In particular, the one in which titania was inserted between the clay layers had a high antibacterial effect.

Each of the antibacterial inorganic coatings of the examples could be baked at a temperature of 200 ° C. or lower after coating, and no crack was generated in the coating film.

[0089]

[Table 1]

[0090]

EFFECT OF THE INVENTION The antibacterial inorganic coating of the present invention has long-term antibacterial performance, can be baked at a temperature of 200 ° C. or lower, and has flexibility, so that the coating film does not crack.

In particular, the antibacterial inorganic coating composition according to any one of claims 7 to 12 of the present invention comprises a component having a photocatalytic function as an antibacterial agent, and a clay mineral having an oxide having a photocatalytic function inserted between layers. Since it contains, the oxygen permeability of the inorganic coating material enhances the antibacterial property and thus has a higher antibacterial property.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location // C08G 77/06 NUB (72) Inventor Naoji Nakagawa 1048 Kadoma, Kadoma, Osaka Prefecture Matsushita Electric Works Co., Ltd. Inside the ceremony company (72) Inventor Kazuo Seto 1048, Kadoma, Kadoma-shi, Osaka Matsushita Electric Works Co., Ltd.

Claims (12)

[Claims] 1. An antibacterial inorganic coating material comprising an inorganic coating material having the following composition and an antibacterial agent. The above-mentioned inorganic paint contains (a) a silicon compound represented by the general formula: Si (OR ¹ ) ₄ and / or colloidal silica in an amount of 20 to
200 parts by weight, (b) 100 parts by weight of a silicon compound represented by the general formula: R ² Si (OR ¹ ) ₃ , and (c)
General formula: containing a silicon compound represented by R ² ₂ Si (OR ¹ ) ₂ in a proportion of 0 to 60 parts by weight, and (d) the weight average molecular weight of the inorganic coating material containing these is 900 in terms of polystyrene. That is all. [The above R ¹ and R ² represent a monovalent hydrocarbon group. ] 2. An antibacterial inorganic paint comprising an inorganic paint having the following composition and an antibacterial agent. The above-mentioned inorganic coating composition comprises (a) 0.001 to 0.5 parts of water relative to X1 mol in colloidal silica in which a hydrolyzable organosilane represented by the following general formula [1] is dispersed in an organic solvent or water. A silica-dispersed oligomer solution of organosilane partially hydrolyzed under the condition of using moles, and R ³ _n SiX _4-n [1] [wherein, R ³ is the same or different and has 1 or 2 substituted or unsubstituted carbon atoms. 8 is a monovalent hydrocarbon group, n is an integer of 0 to 3, and X is a hydrolyzable group. (B) A polyorganosiloxane having a silanol group in the molecule represented by the following formula [2], and R ⁴ _a Si (OH) _b O _{(4-ab) / 2} [2] [In the formula, R ⁴ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and a and b are 0.2 ≦ a ≦ 2 and 0.0001 ≦ b ≦, respectively. 3, a +
It is a number that satisfies the relationship of b <4. (C) a catalyst, and (D) the colloidal silica of the silica-dispersed oligomer solution has a silica content of 5 to 95% by weight.
At least 50 mol% of the hydrolyzable organosilane is an organosilane in which n in the formula [1] is 1, and (e) 1 to 1 of the above silica-dispersed oligomer solution.
9 parts by weight of 9 parts by weight of the above polyorganosiloxane
9 to 1 part by weight. 3. The antibacterial inorganic coating material according to claim 1 or 2, wherein the antibacterial agent contains a component having an elution type antibacterial performance. 4. The component having the elution-type antibacterial performance according to claim 3 is silver, copper, zinc, nickel, palladium, platinum,
The antibacterial inorganic coating material according to claim 3, which is at least one selected from the group consisting of gold, cadmium, mercury, cobalt, and rhodium. 5. The antibacterial inorganic coating material according to any one of claims 1 to 4, wherein the antibacterial agent is a quaternary ammonium salt. 6. The antibacterial agent contains at least one selected from an organic halogen-containing compound, a chlorine-containing compound, and an iodine compound.
Any of the antibacterial inorganic paints. 7. The antibacterial agent contains a component having a photocatalytic function, as claimed in any one of claims 1 to 6.
Any of the antibacterial inorganic paints. 8. The component having a photocatalytic function according to claim 7,
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. , At least one selected from the group consisting of cobalt oxide, rhodium oxide, and rhenium oxide.
The antibacterial inorganic coating material according to claim 7, which is a seed. 9. The antibacterial inorganic coating material according to claim 1, wherein the antibacterial agent is a clay mineral in which an oxide having a photocatalytic function is inserted between layers. 10. The oxide having a photocatalytic function according to claim 9, wherein 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,
The antibacterial inorganic coating material according to claim 9, which is at least one selected from the group consisting of tantalum oxide, manganese oxide, cobalt oxide, rhodium oxide, and rhenium oxide. 11. The antibacterial inorganic coating material according to claim 7, wherein a metal is supported on the component or the oxide having the photocatalytic function. 12. The metal according to claim 11, which is at least one selected from the group consisting of silver, copper, iron, nickel, zinc, platinum, gold, palladium, cadmium, cobalt, rhodium and ruthenium. The antibacterial inorganic coating material according to claim 11.