JPH11181338A - Antibacterial agent for silicon-based paint, antibacterial silicon-based paint composition, coating film thereof, and antibacterial substrate coated therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antibacterial agent which gives an antibacterial coating film showing no color change to yellow or brown even mixed with a silicon- based paint by using a silver (compound) supported on a titanium oxide. SOLUTION: The antibacterial agent is composed of a silver (compound), preferably a silver metal supported on a titanium oxide. The paint composition comprises an organopolysiloxane represented by the formula, a hardening agent comprising an organic metal compound (for example; a dibutyltin dilaurate), the antibacterial agent comprising a silver (compound) supported on a titanium oxide and, if necessary, a silicon-containing vinylpolymer (for example; an acrylsilicon resin) (R<11> is H or 1-4C alkyl; R<12> is H or OR<11> ; R<12> to R<16> are each H, OR<11> or a monovalent hydrocarbon group and at least one of them is preferably a group having trialkylsilyl group comprising three 1-4C alkyl groups bonded to a silicone atom which is directly bonded, without being mediated by an oxygen, to silicone atom of a polysiloxane main chain; and g is 1-100, preferably 1-15.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial agent for a silicon-based coating, an antibacterial silicon-based coating composition, a coating film thereof, and an antibacterial substrate coated with the coating film. Despite the agent being blended, an antibacterial silicon-based coating composition having no discoloration such as yellowing and a coating film formed from the composition, having no discoloration such as yellowing, and having excellent heat resistance, and The present invention relates to an antibacterial substrate coated with the coating.

[0002]

BACKGROUND OF THE INVENTION Conventionally, silicon-based paints containing an organopolysiloxane such as acrylic silicone and a curing agent have been used. The coating film made of this silicon-based paint is excellent in heat resistance and weather resistance, but as the content of organosiloxane contained in this silicon-based paint increases, it becomes harder and harder to damage the cured film. The properties of the coating film (inorganic coating film) made of a paint appear strongly, and the characteristics of the organic coating film tend to appear more strongly, such as the higher the acrylic silicone content, the more difficult it is to crack.

[0003] Like a silicon-based coating film, a fluorine-based coating film tends to be excellent in heat resistance and weather resistance, but has a problem that it is more easily damaged than a silicon-based coating film. By the way, in recent years, antibacterial agents such as silver, silver-based compounds, etc., which are excellent in safety, are used for things that touch human hands, such as panels, curtain walls, etc. An antibacterial paint, such as an epoxy-based or acrylic-based paint, is added.

[0004] If the above-mentioned silicon-based paint containing the above-mentioned antibacterial agent can be used for such applications, it is hardly damaged, and in addition to heat resistance and weather resistance, it is excellent in human safety.
The appearance of painted products with antibacterial properties can also be expected.

However, when the present inventors actually applied a silicon-based paint containing the above silver and silver-based compound as an antibacterial agent to an object to be coated, the resulting silicon-based coating film was an epoxy-based or acrylic-based coating. It has been found that there is a problem that, unlike the case of such a coating film, the color changes to yellow, brown, or the like, and the appearance is remarkably impaired.

Accordingly, the present inventors have conducted intensive studies and found that a silver or silver compound supported on a specific substance is blended with a silicon-based paint composed of an organopolysiloxane and an organometallic compound. The inventors have found that the coating film has excellent heat resistance and weather resistance, is hardly damaged, has antibacterial properties, and does not discolor to yellow, brown, or the like, and has completed the present invention.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems associated with the prior art as described above. It is intended to provide antibacterial agents.

The present invention relates to an antibacterial silicon-based coating composition which is free from discoloration such as yellowing even though a silver-based antibacterial agent such as silver or a silver compound is blended, and is formed from the composition. An object of the present invention is to provide a coating film which is free from discoloration such as discoloration and has excellent heat resistance, and an antibacterial substrate coated with the coating film.

[0009]

SUMMARY OF THE INVENTION The antibacterial agent for a silicon-based paint according to the present invention is characterized by comprising silver or a silver compound supported on titanium oxide.

The antimicrobial silicon-based coating composition according to the present invention comprises:
It is characterized by containing (A) an organopolysiloxane, (B) a curing agent comprising an organometallic compound, and (C) an antibacterial agent comprising silver or a silver compound supported on titanium oxide.

The antimicrobial silicon-based coating composition according to the present invention may further contain a silicon-containing vinyl polymer (a). The coating film according to the present invention is formed from such an antibacterial silicon-based coating composition.

The antibacterial substrate according to the present invention is coated with a coating film comprising the above antibacterial silicon-based coating composition. According to the present invention, despite the fact that silver and a silver-based antibacterial agent such as a silver compound are compounded, there is no discoloration such as yellowing and browning, heat resistance, excellent weather resistance, less damage, and antibacterial properties. An antimicrobial silicon-based coating composition capable of forming a coating film having the following is obtained.

According to the present invention, there is provided a coating film obtained by coating and curing the above coating composition and having the above-mentioned various properties such as no discoloration such as yellowing, and an antibacterial base coated with the coating film. Wood is obtained.

Such an antibacterial silicon-based coating composition is preferably prepared by blending the above component (C) with the component (A) and / or the component (B). To be used as a two-pack type.

[0015]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the antibacterial agent for a silicon-based coating, the antibacterial silicon-based coating composition, its coating film, and the antibacterial substrate coated with the coating film according to the present invention will be specifically described. . [Antimicrobial agent for silicon-based paint and antibacterial silicon-based paint composition] The antibacterial silicon-based paint composition according to the present invention comprises (A) an organopolysiloxane and (B) a curing agent comprising an organometallic compound. (C) an antibacterial agent made of silver or a silver compound supported on titanium oxide (an antibacterial agent for silicon-based paint).

<Organopolysiloxane (A)> In the present invention, an organopolysiloxane (A) having the following reactive functional group (eg, OR ¹¹ group) is used.

[0017]

Embedded image

[In the formula (A), R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹² , R ¹³ , R ¹⁴ , R
¹⁵ and R ¹⁶ each independently represent a hydrogen atom, an OR ¹¹ group or a monovalent hydrocarbon group, and preferably R ^{12 to} R ¹⁶
Is a trialkylsilyl group in which three alkyl groups each having 1 to 4 carbon atoms are bonded to a Si atom, and the silicon atom (Si) in the main chain siloxane bond is not interposed through an oxygen atom; Those directly bonded are desirable. g is 1 to 1
00, preferably an integer of 1 to 15. ] Among such organopolysiloxanes (A),
As g is larger, there is a tendency that shrinkage strain during curing of the antibacterial silicon-based coating composition can be reduced, but the viscosity of the liquid increases,
The handleability of the antibacterial silicon-based coating composition tends to decrease, for example, it is necessary to adjust the viscosity by diluting with an organic solvent or the like. In the present invention, a fluid organopolysiloxane having a molecular weight of generally from 10 ² to 10 ⁵ is used.

The "monovalent hydrocarbon group" in the organopolysiloxane represented by the formula (A) includes a linear or branched alkyl group, a fluoroalkyl group, a vinyl group,
Allyl, alkenyl, phenyl, xenyl, naphthyl, aryl, cyclohexyl, cyclohexenyl, benzyl, aralkyl, araryl, epoxy, aminoalkyl, and the like. Among them, a methyl group, an ethyl group and a phenyl group are preferred. In the present invention, such various organopolysiloxanes may be used alone or in combination of two or more.

The organopolysiloxane (A)
The OR ¹¹ group is important together with a functional group (eg, OR ³ group) of a silicon-containing vinyl polymer described later, for example, in promoting polymerization (crosslinking) after application by moisture curing. That is, the OR ¹¹ group forms a silanol group by a dealcoholation reaction generated by hydrolysis with water, or a polymerization reaction by a dealcoholation reaction with a siloxane having an OH group (that is, silanol) in the presence of a curing regulator. Is important as a functional group that promotes This OR ¹¹
Group, an alkoxy group _{(-OC n H 2n + 1:} n is an integer of from 1 to 10) it is desirable that.

Such an organopolysiloxane (A)
Is contained in the antimicrobial silicon-based coating composition of the present invention in an amount of usually 70 to 98 parts by weight, preferably 90 to 96 parts by weight, based on 100 parts by weight of the nonvolatile components in the antimicrobial coating composition. Is desirable. When the organopolysiloxane (A) having the reactive functional group (eg, OR ³ group) in such an amount is contained in the antibacterial silicon-based coating composition,
The SiO ₂ concentration of the antibacterial silicon-based coating composition can be increased, and the composition can be cured to form a highly densified coating film, which is suitable for nonflammability and flame retardancy.

<Silicon-Containing Vinyl Polymer (a)> The antimicrobial silicon-based coating composition according to the present invention contains the following silicon-containing vinyl polymer (a) together with the polyorganosiloxane (A). Is also good.

That is, one or more ethylenic double bond-containing organosiloxane monomers represented by the following formula (a) (also simply referred to as “organosiloxane monomers and silicon-containing vinyl monomers”) are (co) It is a (co) polymer obtained by polymerization.

(A): R _n · Si · (OR ^X ) _4-n [where n = 1 or 2 in the formula (a), and when n = 1, R
Represents a group having an ethylenically unsaturated group having 2 to 10 carbon atoms, and when n = 2, one of the two Rs represents a group having the above ethylenically unsaturated group, and the rest is the above ethylene A group having an unsaturated group, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aromatic hydrocarbon group in which one part of a hydrogen atom may be substituted with an alkyl group having 1 to 5 carbon atoms, Hydrogen group-containing alkylene group (alkylene group has 1 to 5 carbon atoms)
Wherein a part of the hydrogen atoms in R may be substituted with a halogen atom, and R ^X represents a hydrogen atom, a halogen atom, and a carbon atom having 1 carbon atom which may be partially substituted with a halogen atom. And R 5 to R ^X may be the same or different from each other. Such a silicon-containing vinyl polymer includes an oligomer having a low polymerization degree of about 2 to 3 mer. When the antimicrobial silicon-based coating composition of the present invention is cured, water reacts with an alkoxy group as a functional group in the first stage, and a dealcoholization reaction occurs in the first stage, in a manner similar to the curing reaction of the organopolysiloxane. Occurs to produce silanol groups. Then, in the second step, the alkoxy group of the cross-linking agent reacts with the generated silanol group to cause a condensation reaction by a reaction such as dealcoholation, deoximation, or deacetic acid, and the polymerization proceeds to cure the polymer siloxane having a three-dimensional network structure. It is believed that the body is formed.

The ethylenic double bond-containing organosiloxane monomer (organosiloxane monomer) represented by the above formula (a) is more specifically represented by the following formula (a-
1), (a-2), (a-3), (a-4), (a-5), and (a-6).

[0026]

Embedded image

[In the formula (a-1), R ¹ and R ² represent a hydrogen atom and an alkyl group having 1 to 10 (preferably 1 to 5) carbon atoms, and R ³ represents a halogen atom and 1 carbon atom. Represents an alkyl group of 10 to 10 (preferably 1 to 5), and u represents an integer of 1 to 8. Examples of the organosiloxane monomer represented by the formula (a-1) include γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxy Propyltributoxysilane and the like.

[0028]

Embedded image

[In the formula (a-2), R ¹ , R ² and R ⁴ are represented by the formula (a-
Same as R ¹ of 1) a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (preferably 1 to 5), R ³ is same as R ³ of formula (a-1), a halogen atom, a carbon Represents an alkyl group of the numbers 1 to 10 (preferably 1 to 5), and u represents an integer of 1 to 8. Examples of the organosiloxane monomer represented by the formula (a-2) include γ- (meth) acryloxypropylmethyldimethoxysilane.

[0030]

Embedded image

[In the formula (a-3), R ¹ , R ² and R ³ are the same as those in the case of (a-1). Examples of the organosiloxane monomer represented by the formula (a-3) include vinyltrimethoxysilane and vinyltriethoxysilane.

[0032]

Embedded image

[In the formula (a-4), R ¹ , R ² , R ³ and R ⁴ are the same as in the case of (a-2). As the organosiloxane monomer represented by the formula (a-4), for example, vinylmethyldimethoxysilane and the like can be mentioned.

[0034]

Embedded image

[In the formula (a-5), R ¹ , R ² and R ³ are the same as in the case of (a-1). Examples of the organosiloxane monomer represented by the formula (a-5) include vinyltrichlorosilane, propenyltrichlorosilane and the like.

[0036]

Embedded image

[In the formula (a-6), R ¹ , R ² and R ³ are the same as in the case of (a-1). u shows the integer of 1-8. Examples of the organosiloxane monomer represented by the formula (a-6) include γ- (meth) acryloxypropyltrichlorosilane.

In such an organosiloxane monomer, a part of the alkoxy group may be hydrolyzed to form a hydroxyl group (corresponding to the case where R ^X is a hydrogen atom in the above formula (a)).

[0039] In the present invention, the above-mentioned silicon-containing vinyl polymers, with these organosiloxane monomer, if necessary, the formula: in ^{R 6 COOR 7 ···· (AX)} [ formula (Ax), R ⁶ is A hydrocarbon group having an ethylenically unsaturated group having 2 to ¹⁷ carbon atoms;
Indicate 18 alkyl groups. ], And various monomers such as unsaturated carboxylic acid esters.

Such an unsaturated carboxylic acid ester monomer is a carboxylic acid ester having an ethylenically unsaturated group, and specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, ( Meth) propyl acrylate, (meth) butyl acrylate, and the like.
Methyl (meth) acrylate and ethyl (meth) acrylate are preferably used from the viewpoint of easy availability and physical properties of the resulting coating film.

The average molecular weight of the uncured silicon-containing vinyl polymer [(co) polymer] obtained by (co) polymerizing the unsaturated carboxylic acid ester monomer or the like as required in addition to the above organosiloxane monomer is usually 5,000 to 5,000. 3
0000, preferably about 10,000 to 25,000. In the present invention, such a silicon-containing vinyl polymer can be used alone or in combination of two or more.

In the present invention, the siloxane content (in terms of SiO ₂ ) of the antibacterial silicon-based coating composition is as follows:
There is no particular limitation, and various types are used depending on the application such as non-combustibility / flame retardation or the curing method.

For example, when the antibacterial silicon-based coating composition of the present invention is for baking, a siloxane content (in terms of SiO ₂ ) of, for example, 70% by weight or more is used. When the composition is applied and cured, a cured coating film having particularly excellent weather resistance and stain resistance is obtained. For heating and drying, those having a siloxane content (in terms of SiO ₂ ) of, for example, about 30 to 50% by weight are used, and for room temperature drying, those having about 30 to 40% by weight are used.

In order to obtain an antibacterial silicon-based coating composition having a high siloxane content, such as for baking, the amount of the silicon-containing vinyl polymer used as needed together with the organopolysiloxane may be appropriately increased. The content of the vinyl polymer is, in terms of the nonvolatile content, usually 100 parts by weight of the nonvolatile content in the organopolysiloxane,
It is used in an amount of 40 to 80 parts by weight.

In a preferred embodiment of the present invention,
Along with the luganopolysiloxane (A), silicon-containing vinyl
Methyl as the terminal group of the rimer (including the main chain and side chain)
An alkyl group having 1 to 5 carbon atoms such as
Group, trialkoxysilyl group (alkoxy group: carbon number
1 to 5), preferably a siloxane content (SiO
_Two20% by weight or more (a-i) and silicon-containing
Methyl group, ethyl group, etc.
C1-C5 alkyl group, trialkoxysilyl group
(Alkoxy group: having 1 to 5 carbon atoms), preferably
Siloxane content (SiO_TwoLess than 20% by weight
More preferably 1 to 15% by weight, particularly preferably 2 to 1% by weight.
About 0% by weight (a-ii)
It is desirable.

In the baking type, (a-i) is added to 100 parts by weight of the nonvolatile components in the polyorganosiloxane (A).
Is usually 50 to 80 parts by weight, preferably 60 to 70 parts by weight in terms of nonvolatile components, and (a-ii) is usually 1 to 30 parts by weight, preferably 5 to 10 parts by weight in terms of nonvolatile components. It is desirable to use them in combination in the amounts described above.

In the heat drying type, (a-i) is added to 100 parts by weight of the nonvolatile components in the polyorganosiloxane (A).
Is usually 40 to 70 parts by weight, preferably 50 to 60 parts by weight in terms of nonvolatile components, and (a-ii) is usually 1 to 30 parts by weight, preferably 10 to 20 parts by weight in terms of nonvolatile components. It is desirable to use them in combination in the amounts described above.

In the room temperature drying type, (a-i) is added to 100 parts by weight of the nonvolatile components in the polyorganosiloxane (A).
Is usually 30 to 60 parts by weight, preferably 40 to 50 parts by weight in terms of nonvolatile components, and (a-ii) is usually 1 to 30 parts by weight, preferably 20 to 30 parts by weight in terms of nonvolatile components. It is desirable to use them in combination in the amounts described above.

<Curing Agent (B) Composed of Organometallic Compound>
The antimicrobial silicon-based coating composition contains a curing agent or a curing accelerator (B) composed of an organometallic compound.
This organometallic compound contributes to the crosslinking and curing of the uncured polyorganosiloxane and the silicon-containing vinyl polymer after application of the antibacterial silicon-based coating composition, and as such an organometallic compound, specifically, Examples thereof include liquid alkoxides having a functional side chain OR ^d group and represented by the following formulas (B1) and (B2).

R ²² _p T · (OR ^d ) _{3 -p} (B1) R ²³ _m Q · (OR ^d ) _{4 -m} (B2) [Equations (B1) and (B2) In the formula, T is an aluminum or boron atom, Q is a silicon, titanium or zirconium atom, R ^d is an alkyl group having 1 to 4 carbon atoms, and R ²² is a hydrogen atom or is the same or different. Represents an alkyl group having 1 to 4 carbon atoms, and R ²³ is
Hydrogen atom, OR ^d group, an organic group having an amino group, an acyloxy group, an oxime group or a monovalent hydrocarbon group and these groups (hydrogen atoms, except the monovalent hydrocarbon group) and formed by bonding group, And p represents 1 or 2, and m represents an integer of 1 to 3. When T in the formula (B1) is an aluminum atom, p is 0
In case R ^d is as isopropyl or secondary butyl group and T is a boron atom, with p is 0, R ^d
Is preferably an organometallic compound having a trialkoxy group such as a methyl, ethyl or butyl group.

When Q in the formula (B2) is a silicon atom, R
Tetramethyl or ethyl orthosilicate where ²³ is a methoxy or ethoxy group, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, γ-glycidoxypropylmethoxysilane, dimethyl Methyl trifluoropropylsilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, γ- (2-aminoethyl)
Organometallic compounds such as aminopropyltriethoxysilane are preferred.

When Q in the formula (B2) is a titanium atom,
Organometallic compounds such as tetra-i-propyl titanate and tetra-n-butyl titanate are preferred. Equation (B)
When Q in 2) is a zirconium atom, an organic metal compound such as tetraethyl zirconate, tetra-i-propyl zirconate, or tetra-n-butyl zirconate is preferred.

These organometallic compounds are preferably monomers in order to exhibit a crosslinking effect. However, even when a compound such as a dimer, which has begun polymerization, is partially used in place of the monomer, the crosslinking reaction is effected. Speed can be controlled.

Further, in the present invention, as the organometallic compound, in addition to the above, those comprising the following metal chelates can be exemplified. Specifically, for example, zinc naphthenate, aluminum trimethoxide, aluminum tri-tris (acetylacetate), aluminum tri-n-butoxide, diacetyltin diacetate, dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate And organic metal compounds such as diacetyltin dioctoate and tin octylate.

In the present invention, among these organometallic compounds, the formula (B2) is preferable, and the formula (B2) is more preferable.
An organometallic compound in which Q is a silicon atom in 2) is preferably used from the viewpoint of crack resistance of a coating film obtained.

In the present invention, in addition to the above-mentioned metals, Cu, F
e, Pb, Cr, Co, Mn, Mo, Ni and the like. These elements are generally colored, and depending on the purpose, a compound containing these elements and the compound represented by the formula (B)
You may use together with the organometallic compound shown to 1) and (B2).

These organometallic compounds are used with respect to 100 parts by weight of the nonvolatile components in the organopolysiloxane (A).
The organic metal compound is used in an amount of 0.01 to 50 parts by weight, preferably 0.05 to 40 parts by weight in terms of the active ingredient. When the organometallic compound is used in such an amount, the curing conditions of the antimicrobial silicon-based coating composition can be controlled, and the coating can be uniformly solidified, and a coating film excellent in solvent resistance and stain removal resistance can be formed.

<Antibacterial agent for silicon-based paint (C)> The antibacterial agent for silicon-based paint according to the present invention comprises silver or silver compound (C) supported on titanium oxide. The cured film obtained by applying and curing the antibacterial silicon-based coating composition containing such an antibacterial agent has excellent heat resistance, weather resistance, hardly causes discoloration such as yellowing and browning, and is safe. Excellent in properties and antibacterial properties.

The silver compound may be either organic or inorganic and includes, for example, silver nitrate and silver oxide. Usually, silver metal is preferably used. As such a silver-based antibacterial agent, trade name: "Gintech A121"
(Manufactured by Kawakaku Giken Co., Ltd.).

Among the above antibacterial agents, an antibacterial silicon-based coating composition containing an inorganic antibacterial agent has excellent heat resistance and durability, and is effective against a wide range of bacterial species such as Escherichia coli and Staphylococcus aureus. In addition, antibacterial silicon-based paint compositions containing an organic antibacterial agent have a fast-acting property, and are resistant to discoloration. Tends to be excellent. In the present invention, these antibacterial agents can be used alone or in combination of two or more.

Such an antibacterial agent (C) for a silicon-based paint is
Usually 0.2 to 1.0 part by weight, preferably 0.4 to 1.0 part by weight, based on 100 parts by weight of the organopolysiloxane (A) (62% non-volatile content) which is a component contained in the antibacterial silicon-based coating composition. It is used in an amount of about 0.6. When the amount of the silver-based antibacterial agent (C) is less than 0.2 parts by weight, the effect of adding the same is poor, and when it exceeds 2 parts by weight, the state of the coating film surface tends to be poor.

The antimicrobial silicon-based coating composition according to the present invention comprises the above-mentioned organopolysiloxane (A), (if necessary, a silicon-containing vinyl polymer (a)), (B) a curing agent comprising an organometallic compound, (C) An antibacterial agent comprising silver or a silver compound supported on titanium oxide is contained. In a particularly preferred embodiment of the present invention, the organopolysiloxane (A) contains the antibacterial silicon-based coating composition 100 The curing agent (B) is used in an amount of usually 15 to 30 parts by weight, preferably 18 to 22 parts by weight, and the curing agent (B) in an amount of 5 to 15 parts by weight, preferably 8 to 12 parts by weight. C) is 0.2 to
1.0 parts by weight, preferably from 0.4 to 0.6 parts by weight, optionally containing silicon-containing vinyl polymer (a)
Is desirably contained in an amount of 14 to 18 parts by weight.

When the organopolysiloxane (A) is contained in the above amount in the antibacterial silicon-based coating composition, the film-forming property tends to be excellent, and the curing agent (B) is contained in the above amount. When it is contained, the drying and curing speed tends to be improved, and when the antibacterial agent (C) is contained in the above amount, the antibacterial action tends to be excellent.

Such an antibacterial silicon-based coating composition is obtained by mixing and stirring the above components in an arbitrary order. In addition, such an antibacterial silicon-based coating composition is prepared, for example, by mixing the antibacterial agent (C) with the organopolysiloxane (A) and / or the curing agent (B), preferably the antibacterial agent (C).
Is mixed with the organopolysiloxane (A) and stored and transported as a two-pack type. At the time of use, a mixture of the organopolysiloxane (A) and the antibacterial agent (C) is combined with the curing agent (B). It is desirable to use it. In addition, it is preferable that the silicon-containing vinyl polymer (a) to be blended if necessary is blended with the organopolysiloxane (A).

<Optional Components> The antimicrobial silicon-based coating composition according to the present invention may contain various components other than those described above, which can be blended into ordinary coating materials.

Examples of such optional components include, in addition to pigments (colorants), activators, fillers, etc., solvents, solvents, modifiers, non-crosslinkable polymers, curing regulators, and the like described below.
Optional components such as pigments (coloring agents), activators, and fillers can be in the form of powder, bulk,
Any shape such as a flake shape and a fiber shape can be taken.

Examples of pigments (including colorants) include inorganic carbon black, titanium dioxide, iron oxide, iron hydroxide, red iron oxide, chromium oxide, graphite, ultramarine, various alloys, white carbon, alumina, fused alumina, Zinc oxide,
Magnetic iron oxide, boron nitride, silicon carbide, clays; organic insoluble azo pigments, soluble azo pigments, condensed polycyclic pigments, quinacridone pigments, isoindolinone pigments, cyanine blue, cyanine green, and the like.

Examples of the activator include boric acid-containing compounds, lead-containing compounds, chromic acid-containing compounds,
Phosphoric acid-containing compounds and the like. When such an activator is previously blended in the antibacterial silicon-based coating composition of the present invention, when the object to be coated is a metal such as iron, a coating comprising the antibacterial silicon-based coating composition is used. The adhesion between the film and the object to be coated is improved, and the corrosion resistance tends to be improved.

Specific examples of the filler include metals and alloys such as stainless steel, silicon, zinc, aluminum, and iron. These may be in the form of paste, flake, or powder.

In addition, glass, ceramics, diamond, silicon oxide (silica sand, silica stone, silica, etc.), magnesium, calcium carbonate, zircon sand, various clays, calcined clay (eg, bauxite, montmorillonite, kaolin, etc.), gypsum , Calcium phosphate, magnesium phosphate, barium sulfate, aluminum fluoride, calcium silicate, magnesium silicate, barium silicate, barium carbonate, barium hydroxide, aluminum silicate, talc,
Powders such as mica and fly ash may be mentioned.

In the present invention, these components can be used alone or in combination of two or more. Among these optional components, for example, a pigment (colorant), an activator, and a filler are each usually used with respect to 100 parts by weight of the nonvolatile components in the organopolysiloxane contained in the antibacterial silicon-based coating composition. 500 parts by weight or less, preferably 40 parts by weight
It is used in an amount of 0 parts by weight or less.

The solvent is substantially inert to each component in the antibacterial silicon-based coating composition, as long as it can dissolve or disperse components such as a polymer in the composition.
From the viewpoint of coating workability and the like, conventionally known ones can be widely used.

Specific examples of such a solvent include hydrocarbon solvents such as toluene, xylene, pentane, hexane and heptane; acetone, methyl ethyl ketone and the like.
Ketones such as methyl isobutyl ketone; esters such as ethyl acetate, propyl acetate and butyl acetate; dioxane;
Alcohols such as ethanol, butanol, and isopropyl alcohol; and the like. These solvents can be used alone or in combination of two or more depending on the curing method or the like.

In consideration of the dissolving and dispersing properties of each of the components and the workability of coating the antibacterial silicon-based coating composition, these solvents have a non-volatile content of 1 in the antibacterial silicon-based coating composition.
It is usually used in an amount of 10 to 2000 parts by weight, preferably 20 to 1000 parts by weight, based on 00 parts by weight.

As a modifying agent, a leveling agent, a dispersant,
Conventionally known ones such as an antifoaming agent, a viscosity-imparting agent, and a storage stabilizer, which are usually blended in a paint, may be used. Examples of the non-crosslinkable polymer include a solvent-type or dispersion-type organic polymer, which can form a solidified body by volatilization of the coexisting solvent at ordinary temperature or under heating. Are cellulose resins (eg, nitrocellulose, acetylcellulose, acetylbutylcellulose, ethylcellulose, etc.), acrylic resin, urethane resin, vinyl chloride resin, vinyl chloride organosol dispersion, fluorine resin, alkyd resin , Vinyl acetate resin, styrene-butadiene resin,
Silicone resin, colloidal silica, alumina dispersion, or the like is used.

As the curing regulator, conventionally known curing regulators can be used, but in the present invention, the formula: R ⁴ COO
H... (AY) [In the formula (AY), R ⁴ is a group having 1 to 1 carbon atoms.
11 hydrocarbon groups. Or a anhydride thereof.

Such a carboxylic acid or an anhydride thereof may be a saturated or unsaturated compound. Specifically, a saturated fatty acid having a monovalent carboxyl group such as acetic acid, pyruvic acid or trimethyl Acetic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, caproic acid,
Enantylic acid, caprylic acid (octylic acid), berargonic acid, undecanoic acid, and succinic anhydride, glutaric anhydride, trimethylsuccinic acid, which is a saturated fatty acid having a divalent carboxyl group, phthalic anhydride, and glycolic acid, which is an oxyacid And the like. In addition, unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, and tiglic acid are exemplified. In the present invention, these carboxylic acids or their anhydrides can be used alone or in combination of two or more.

<Coating Method> The antibacterial silicon-based coating composition according to the present invention may be in any form of mortar, paste, liquid, paint, etc. It is coated (painted).

The coating method is not particularly limited, and a conventionally known method can be employed. For example, spraying, airless spray, air spray, brush coating, ironing, roller coating (roll coater), dipping, pulling up, and flowing Methods such as coating (flow coater), plating, electrostatic coating, and the like can be employed.

Further, drying and drying of the antibacterial silicon-based coating composition
The curing method varies depending on the curing agent in the antibacterial silicon-based coating composition, the type of catalyst, and the like. For example, baking (e.g., holding at a temperature of 200 to 230C for 20 to 30 minutes), drying by heating ( Example: 5-1 at a temperature of 120-150 ° C
Various methods such as drying for 5 minutes) and drying at room temperature.

The material of the object on which such a coating film is formed is not particularly limited, and examples thereof include wood, concrete, metal, plastic, and non-combustible building materials.
In addition, you may apply in combination with various undercoats, binders, primers, etc. according to the material of such to-be-coated material.

Examples of the antibacterial substrate obtained by applying and curing such an antibacterial silicon-based coating composition on an object to be coated include a member for a house (eg, a panel, a curtain wall, a partition, etc.) and a large public steel. There is a wide range of structures that can be touched by human hands, such as structures.

Such an antibacterial base material is excellent in heat resistance, weather resistance, antibacterial property and safety, is hardly damaged, and hardly discolors to yellow, brown or the like.

[0084]

According to the present invention, there is provided an antibacterial agent for a silicon-based paint which contains silver or a silver-based compound and does not cause discoloration such as yellowing or browning in the silicon-based coating film.

According to the present invention, silver or a silver-based compound excellent in safety to the human body is contained as an antibacterial agent, and a coating film formed by application and curing is excellent in heat resistance and weather resistance and is not scratched. It is possible to obtain a silicon-based paint that is difficult to discolor to yellow, brown, etc.

[0086]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to such examples.

In the following Examples and Comparative Examples, “parts” means “parts by weight”. Examples below,
The trade names, compositions, physical properties, manufacturers, etc. of the components used in the comparative examples are as follows.

<(A) Acrylic silicone resin> (1) "ASC-721" (MMA-γ-methacryloxypropyltrimethoxysilane, molecular weight of 20,000 to 25,000, manufactured by Ohtake Chemical) (2) "CF4177" (Acrylic silicone phenyltrimethoxysilane, molecular weight 20,000, manufactured by Toray Dow Corning) <(b) Methylphenyl polysiloxane resin> (1) "Silicone KR-217" (methylphenyl silicone intermediate, molecular weight 5000, manufactured by Shin-Etsu Chemical Co., Ltd.) (2) "Silicone SH840" (methylphenyl silicone intermediate, molecular weight 5000, manufactured by Dow Corning Toray) <(c) Methyl silicate resin> (1) "M silicate 51" (methoxypolysiloxane,
(Molecular weight 470, manufactured by Tama Chemical) Methyl silicate resin:

[0089]

Embedded image

(2) "Silicate 45" (ethoxypolysiloxane, molecular weight 900, manufactured by Tama Chemical) <(d) Rutile-type titanium oxide> (1) "Titanium R-960" (super weather-resistant rutile titanium, DU
<(E) Antibacterial agent> (1) "GinTech A-121" (titanium oxide carrying silver, manufactured by Kawakaku Giken) (2) "Novalon AG300" (zirconium phosphate carrying silver, Toa Gosei) (3) "Antimicrobial ceramic" (ceramic carrying silver, manufactured by Shinto Kogyo) ) "BYK-163" (dispersant, manufactured by Bykche) (3) "Dispalon A630-20X" (precipitation inhibitor, manufactured by Kusumoto Kasei) (4) "Disparon LS-015" (leveling agent, manufactured by Kusumoto Chemical) (g) Solvent> Xylene, isobutyl alcohol, butyl acetate <(h) Curing accelerator> (1): Any one of (a) to (c) is used. (B) "Neostan U-200" (dibutyltin diacetate, manufactured by Nitto Kasei) (b) "Neostan U-100" (dibutyltin dilaurate, manufactured by Nitto Kasei) (c) "TBZr" (tetrabutylzirconium, Nitto Kasei) Made)

[0091]

Example A An antibacterial silicon-based coating composition having the following composition was prepared as follows.

<Blending composition> (a) Acrylic silicone resin 16 parts (b) Methylphenylpolysiloxane resin 15 parts (c) Methyl silicate resin 6 parts (d) Rutile type Titanium oxide 20 parts (e) Antibacterial agent (type: titanium oxide carrying silver) 0.5 parts (f) Additives for paint (dehydrating agent, dispersant, precipitation inhibitor, leveling agent) 10 parts (g) Solvent (type: xylene, isobutyl alcohol, butyl acetate) 32.5 parts (subtotal 100 parts by weight) (h) Curing accelerator 10 parts (total) 110 parts by weight)

<Method for Preparing Antimicrobial Silicone Coating Composition>
At room temperature, 20 parts of rutile-type titanium oxide premixed with a dehydrating agent, 16 parts of a pigment dispersant, and 20 parts of a solvent were added to 16 parts of an acrylic silicone resin, kneaded and mixed, and 15 parts of a methylphenylpolysiloxane resin and 15 parts of a methylsilicate resin were added. Six parts were added and mixed with stirring to prepare a white paint. To this white paint, 12.5 parts of the remaining solvent, 0.5 parts by weight of the remaining additives and the antibacterial agent were added, and the mixture was stirred with a disper (stirred so as to be dispersed) to obtain an antibacterial silicon-based coating composition (base). Was.

[0094] <Preparation of test plate> article to be coated SUS304 the ^#
After roughening with a sandpaper of 120 to 240, a mixture of 100 parts of an antibacterial silicon-based coating composition (main agent) and 10 parts of a curing accelerator on the roughened surface of the object to be coated is dried. The film was applied by air spray so that the thickness of the coating film became 25 to 30 μm, and was forcedly dried at 180 ° C. for 20 minutes.

The test plate was subjected to a pencil scratch test, an adhesion test, and a test method according to the test methods and evaluation criteria shown in Tables 3 and 4 below.
Water resistance, boiling water resistance, antibacterial properties against Escherichia coli and MRSA, and accelerated weather resistance were evaluated. The results are shown in Tables 3 and 4.

Tables 1 and 2 also show the composition of the antibacterial silicon coating composition (coating composition).

[0097]

Test Examples B to R In Example A, the composition was as shown in Tables 1 to 3.
2, except that it was changed as shown in FIG.
A test plate was prepared and the same test as in Example A was performed.

The results are shown in Tables 3 and 4. In Tables 1 to 4, test numbers A, E, I, M, Q and R are examples of the present invention, and the others are comparative examples.

[0099]

[Table 1]

[0100]

[Table 2]

[0101]

[Table 3]

[0102]

[Table 4]

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI C09D 5/14 C09D 5/14 183/04 183/04 (72) Inventor Koji Morimoto Character Mikami, Yasu-cho, Yasu-gun, Shiga Prefecture 2306 7 China Paint Co., Ltd.

Claims (5)

[Claims] 1. An antibacterial agent for a silicon-based paint, comprising silver or a silver compound supported on titanium oxide. 2. A composition comprising (A) an organopolysiloxane and (B)
An antibacterial silicon-based coating composition comprising: a curing agent comprising an organometallic compound; and (C) an antibacterial agent comprising silver or a silver compound supported on titanium oxide. 3. The antibacterial silicon-based coating composition according to claim 2, further comprising a silicon-containing vinyl polymer. 4. A coating film formed from the antibacterial silicon-based coating composition according to claim 2. 5. An antibacterial substrate coated with the coating film according to claim 4.