JP2003003068A - Curable composition having antibacterial and mildew- proof properties and its cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable composition which exhibits superior antibacterial, mildew-proof and alga-proof properties for a prolonged period with the original characteristics of curable organosilicon compounds not being damaged and which gives a cured product excellent in transparency, causes no discoloration on heating, and possesses antibacterial and mildew-proof properties permitting the safe use in environmental and hygienic aspects. SOLUTION: The composition contains, as the major components, (A) 100 pts.wt. of a curable organosilicon compound selected from silane compounds and silicone resins and (B) 0.05-20 pts.wt. of an antibacterial zeolite containing 0.1-15 wt.% of silver ions, and is characterized in that the cured film in 40-60 μm thickness has a haze value of 30 or less in the light transmission test.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable composition having antibacterial and antifungal properties, whereby a cured molded article of the curable composition or a coating product obtained by coating and curing the curable composition. It is possible to give effects such as improvement of the environment of the adhered body, extension of product life, improvement of environmental hygiene, etc. Furthermore, since the cured molded body and the coating have excellent transparency, curing that does not impair the design of the product Composition and a cured product thereof.

[0002]

2. Description of the Related Art Unlike other organic resins, silicone resins are excellent in heat resistance, weather resistance, water resistance, flame retardancy, etc. and can form a surface of high hardness. Therefore, a curable silicone resin having a crosslinkable group such as an alkoxy group or a silanol group bonded to a silicon atom in the molecule is used as a surface protective material for various base materials, heat resistant paint, weather resistant paint, water repellent, various binders, etc. Widely used in various applications and fields. In recent years, it has been used as a binder of a hydrophilicity-imparting coating composition for the purpose of preventing surface stains,
As a key top material for mobile phones and small terminals, its application is expanding to applications other than coating.

In particular, recently, a coating material of a curable silicone resin is applied to a portion of a building material such as a wall material or a floor material, a marine structure, a river structure or a public facility in contact with sea water or fresh water to protect the surface. Attempts have been made to impart functions such as denaturation and modification, and from the viewpoint of further enhancing functionality, there is a demand for simultaneously imparting antibacterial properties, fungicidal properties and algae proof properties. In this case, since the silicone resin is a chemically and physiologically inactive substance, it is necessary to add an antibacterial agent, a fungicide or an algae inhibitor separately, and generally, a benzimidazole compound or the like is used. Organic chemical agents such as organic nitrogen compounds, organic sulfonyl halogen compounds such as iodomethylsulfonyl compounds, organic halogen compounds, organic nitrogen halogen compounds, organic nitrogen sulfur compounds such as methylthiotriazine compounds have been used. But,
These drugs are used for temperature change, humidity change, light such as ultraviolet rays,
Or, since it is affected by trace elements in the environment and is altered, there is a problem in the sustainability of antibacterial and antifungal effects. Also,
Some of these organic drugs reduce or inhibit the curability of the silicone resin, and further, there are environmental health problems such as acute toxicity, skin irritation, eye irritation, and fish toxicity. Not a little, there was also a problem that the use and the amount used are limited.

[0004] In order to solve these problems, coating and encapsulation of the above-mentioned organic chemicals have been attempted, and measures have been taken such as adding or carrying an active substance to the silicone resin, but the cost is high. The organic antibacterial agents and fungicides are buried in the silicone resin and do not exert their effects. The silicone resin loaded with and loaded with an active substance deteriorates its effects before it is actually used. However, it is difficult to store, and when a curable silicone resin is heat-cured, the organic antibacterial agents and fungicides contained inside deteriorate and their effect remarkably deteriorates, resulting in discoloration of the cured silicone resin. There was a problem.

In addition, since the silicone resin also has an inorganic property and is essentially incompatible with organic antibacterial agents and fungicides, there is a problem that the obtained cured product is inferior in transparency. there were.

Recently, inorganic antibacterial agents and antifungal agents have been developed. For example, JP-A-5-1226 discloses a water-soluble solution containing one or more ions of silver ion, zinc ion and copper ion. Examples of organic glass, JP-A-2-20559 and JP-A-4-93360 propose an example in which protein silver is added, and JP-A-4-93360 in which at least one of ZnO, MgO and propionate is added. However, in any case, it is not possible to sufficiently support the ions, causing discoloration of the silicone resin, or significantly lowering the supporting ability by treating at a high temperature, which loses its effect,
There have been various problems such as the ones that need to be added in large amounts to maintain antibacterial and antifungal properties, and those that cannot be added for food hygiene.

The present invention has been made to solve the above-mentioned drawbacks, and exerts excellent antibacterial properties, antifungal properties, and antialgal properties for a long period of time without impairing the original properties of the curable organosilicon compound. A curable composition is provided, and the obtained cured product has excellent transparency and does not discolor even when heated,
It is an object of the present invention to provide a curable composition having antibacterial and antifungal properties that can be safely used in terms of environment and hygiene, and a cured product thereof.

[0008]

Means for Solving the Problems and Modes for Carrying Out the Invention As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that 0.1-15 wt% of silver ion is added to the curable composition. % By containing a zeolite containing therein, a curable composition in which such a silver ion-containing zeolite is dispersed is obtained, and a cured product of this silver ion-containing zeolite dispersion-curable composition has excellent antibacterial properties and antifungal properties. In addition, the curable composition does not change its antibacterial property or mold proofing property due to temperature changes when curing or curing, environmental changes such as humidity changes or ultraviolet rays, and is curable even when the zeolite is dispersed. It was found that the above characteristics are not hindered and the original characteristics of the organosilicon compound are sufficiently maintained. Furthermore, it was confirmed that the cured product of the silver ion-containing zeolite dispersion-curable composition thus obtained has excellent transparency, does not discolor even by heating, and is safe in terms of environmental hygiene. The present invention has been completed.

Therefore, the present invention provides a curable organosilicon compound (A) selected from silane compounds and silicone resins,
In particular, (A-1) the following general formula (1) R ¹ _a Si (OR ² ) _4-a (1) (In the formula, R ¹ may be the same or different and may be a substituted or unsubstituted monovalent hydrocarbon group. , R ² represents an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group, or an acyl group, respectively, and a is a number of 0, 1 or 2, or a partial hydrolysis thereof. One or a mixture of two or more kinds of decomposition condensates, or (A-2) the following general formula (2) R ¹ _a SiX _4-a (2) (wherein, R ¹ may be the same or different, or Unsubstituted monovalent hydrocarbon group, a is a number of 0, 1 or 2, X is an OR ² group or a halogen atom, and R ² is an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group. Or an acyl group), and hydrolyzed one or more silanes represented by the formula (1) or two or more thereof. The following general formula (3) R ¹ _b Si (OH) _c (OR ² ) _d O _{(4-bcd) / 2} (3) (wherein R ¹ and R ² are the same as above) , B, c and d
Is 0.2 ≦ b ≦ 1.8, 0 <c ≦ 0.5, 0 ≦ d ≦
It is a number that satisfies 0.5 and 0.5 ≦ b + c + d ≦ 2.5. (1) 100 parts by weight of a curable organosilicon compound comprising one or a mixture of two or more silanol group-containing silicone resins, and (B) an antibacterial zeolite containing 0.1 to 15% by weight of silver ion. Hardening having antibacterial and antifungal properties, characterized in that it has a Haze value of 30 or less in a total light transmission test of a cured coating having a coating thickness of 40 to 60 μm and containing 0.05 to 20 parts by weight as a main component. A sex composition is provided.

Further, there is provided a cured product obtained by curing these curable compositions having antibacterial and antifungal properties.

The present invention will be described in more detail below.
The main component (A) of the curable composition of the present invention is a curable organosilicon compound selected from curable silane compounds and silicone resins. As such a curable organosilicon compound, a compound composed of one or a mixture of two or more of (A-1) a silane compound represented by the following general formula (1) or a partial hydrolysis-condensation product thereof is preferable. R ¹ _a Si (OR ² ) _4-a (1)

R ¹ in the above general formula is a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different, and preferably has 1 to 30 carbon atoms, particularly 1 to 10 carbon atoms. Specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group and a decyl group, a cycloalkyl group such as a cyclohexyl group, an alkenyl group such as a vinyl group and an allyl group, a phenyl group and a tolyl group. Such as aryl groups, or a chloromethyl group in which a part or all of the hydrogen atoms of these groups are substituted with halogen atoms, a chloropropyl group,
Trifluoropropyl group, cyanoethyl group substituted with cyano group, glycidoxypropyl group substituted with epoxy group, epoxycyclohexylethyl group, methacryloxypropyl group substituted with (meth) acryl group, acryloxypropyl group, etc. , An aminopropyl group substituted with an amino group or an aminoalkylamino group, an aminoethylaminopropyl group, and a mercaptopropyl group substituted with a mercapto group.

Similarly, R ² in the general formula (1) is an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group or an acyl group, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group. Examples thereof include alkyl groups such as butyl group, isobutyl group and hexyl group, alkoxyalkyl groups such as methoxyethyl group, ethoxyethyl group, butoxyethyl group, methoxypropyl group and ethoxypropyl group, and acyl groups such as acetyl group.

Further, a in the general formula (1) is a number of 0, 1 or 2, such as the curability of the composition, the hardness of the cured product, and the adhesion to the base material for coating. From the viewpoint, it is preferable that the ratio of the silane compound with a = 1 and the partial hydrolysis-condensation product thereof in the component (A) is 30 mol% or more.

Specific examples of such a silane compound and its partial hydrolysis-condensation product include tetramethoxysilane and
Tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltriacetoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, cyclohexyltrimethoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, allyltrimethoxysilane,
Phenyltrimethoxysilane, phenyltriethoxysilane, γ-chloropropyltrimethoxysilane, 3,
3,3-trifluoropropyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, cyanoethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4 -Epoxycyclohexyl)
Ethyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane,
γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N
-Β (aminoethyl) γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methylvinyldimethoxysilane, diphenyldimethoxy Silane, diphenyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, methylnonafluorohexyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxy Silane, γ-acryloxypropylmethyldimethoxysilane, N-β (aminoethyl) γ-
Examples thereof include alkoxysilanes such as aminopropylmethyldimethoxysilane or acyloxysilanes, and partially hydrolyzed condensates thereof.

In this case, the partially hydrolyzed condensate is a disiloxane unit obtained by reacting 2 moles of the above-mentioned alkoxysilane (2 moles of alkoxysilane with 1 mole of water to eliminate 2 moles of alcohol). ) To 100-mer, preferably 2 to 50-mer, can be preferably used, and it is also possible to use a partial cohydrolysis condensate obtained by using two or more kinds of alkoxysilanes as raw materials. As the curable composition (A) of the present invention, the above-mentioned silane compound or a partial hydrolysis-condensation product thereof may be used alone, or two or more kinds of silane compounds or two or more kinds of partial hydrolysis-condensation products. Alternatively, the silane compound and the partial hydrolysis-condensation product may be used in combination.

The component (A) of the curable composition of the present invention includes (A-2) one or more silanes represented by the following general formula (2) or a partial hydrolysis-condensation product thereof. Those comprising one kind or a mixture of two or more kinds of the silanol group-containing silicone resin represented by the following general formula (3) obtained by hydrolyzing and condensing are also preferably used. R ¹ _a SiX _4-a (2) R ¹ _b Si (OH) _c (OR ² ) _d O _{(4-bcd) / 2} (3)

Here, R in the above general formulas (2) and (3)
¹ is a substituted or unsubstituted monovalent hydrocarbon group which may be the same as or different from R ¹ in the general formula (1). Further, in the general formula (2), a is a number of 0, 1 or 2, X is an OR ² group or a halogen atom such as a chlorine atom, a fluorine atom or a bromine atom, and R ² is the above general formula ( Similar to R ² in 1), it is an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group or an acyl group.

Specific examples of such silanes include the above-mentioned alkoxysilanes and acyloxysilanes exemplified as the silane compound, and chlorosilanes in which those alkoxy groups or acyloxy groups are replaced with halogen atoms. From the viewpoint of easiness of procurement and cost, it is preferable to use chlorosilane or methoxysilane, and a partial hydrolysis-condensation product of these silanes may be used. They can be used alone or in combination of two or more.

Further, R ² in the general formula (3) is an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group or an acyl group, like R ² in the general formula (1). In the OR ² group, X in the general formula (2) is O
When it is an R ² group, it is an alkoxy group or an acyloxy group remaining after hydrolysis, and when X is a halogen atom, it is produced by reaction with the alcohol used as a solvent during hydrolysis, It is an alkoxy group or an acyloxy group remaining inside. Further, b, c and d are
0.2 ≦ b ≦ 1.8, 0 <c ≦ 0.5, 0 ≦ d ≦ 0.
5 and 0.5 ≦ b + c + d ≦ 2.5, preferably 0.5 ≦ b ≦ 1.6 and 0 <c ≦ 0.
3, 0 ≦ d ≦ 0.3, and 0.7 ≦ b + c + d ≦ 2.
It is a number that satisfies 2.

The above-mentioned silane or a partial hydrolyzate thereof is hydrolytically condensed to obtain a silanol group-containing silicone resin represented by the general formula (3), for example, as described in JP-A-4-180926. The method described above can be easily carried out, that is, a method in which silane or a partial hydrolyzate thereof is stirred with water and a catalyst and hydrolyzed and condensed by mixing. Examples of the above catalyst include acids such as hydrochloric acid, sulfuric acid, methanesulfonic acid and p-toluenesulfonic acid, hydroxides of alkali metals or alkaline earth metals such as NaOH, KOH and Ca (OH) ₂ , triethylamine and tetraethylammonium. Examples include alkaline organic substances such as hydroxide. When chlorosilanes are used, hydrochloric acid produced as a by-product acts as a catalyst.

The temperature and reaction time of the hydrolysis condensation reaction are
It may be appropriately determined according to the characteristics of the raw material used and the required product, but is usually 10 to 150 ° C. and 1 to 29 hours. In the reaction, a solvent may be used if necessary. Solvents that can be used include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane and octane, methanol, ethanol, 2
-Alcohols such as propanol and isobutanol, and ketones such as acetone and methyl ethyl ketone.

After reaction, the silanol group-containing silicone resin is neutralized by adding an alkali or an acid to stop the reaction, and then washed with water, filtered, distilled under atmospheric pressure or distilled under reduced pressure as a by-product. It can be obtained by removing a solvent, a solvent, or the like, or by further performing a polycondensation reaction to increase the molecular weight. The weight average molecular weight of the obtained silanol group-containing silicone resin is usually 500 to 1,000.
It is in the range of 10,000, but 1,000 to 100,000.
It is preferably 0. Specific examples of the silanol group-containing silicone resin thus obtained include methylpolysiloxane, phenylpolysiloxane, methylphenylpolysiloxane, and the like.

The curable composition of the present invention contains silver ion in an amount of 0.1 to 0.15 in order to impart antibacterial and antifungal properties as described above.
A zeolite containing 15% by weight is blended.

In this case, the zeolite may be natural zeolite or synthetic zeolite. Zeolite is generally an aluminosilicate having a three-dimensional skeleton structure, and can be represented by the following general formula XM _{2 / n} O · Al ₂ O ₃ · YSiO ₂ · ZH ₂ O.

Here, M represents an ion-exchangeable ion, and is usually a monovalent or divalent metal ion. n is the valence of the metal ion. X and Y are metal oxide and silica coefficients, respectively, and Z is the number of crystal waters. Specific examples of the zeolite include, for example, A-type zeolite, X-type zeolite, Y-type zeolite, T-type zeolite, high silica zeolite, sodalite, mordenite, analcime, clinobuchironite, chabazite, and erionite. However, the present invention is not limited to these. The ion exchange capacity of these exemplary zeolites is
A-type zeolite 7 meq / g, X-type zeolite 6.
4 meq / g, Y-type zeolite 5 meq / g, T-type zeolite 3.4 meq / g, sodalite 11.5 m
eq / g, mordenite 2.8 meq / g, analcime 5 meq / g, clinobutilonite 2.6 meq /
g, chiabasite 5 meq / g, erionite 3.8 m
eq / g, and both have a sufficient capacity for ion exchange with ammonium ions and silver ions.

The antibacterial zeolite used in the present invention is
Ion-exchangeable ions in the zeolite, such as sodium ion, calcium ion, potassium ion,
A part or all of magnesium ions, iron ions and the like are replaced with silver ions. Further, in addition to silver ions, other antibacterial metal ions may be contained, and examples of such antibacterial metal ions include copper, zinc, mercury, lead, tin,
Ions of bismuth, cadmium, chromium or thallium,
Preference is given to the ions of copper or zinc.
Further, it is preferable that ammonium ion is substituted in addition to silver ion.

From the viewpoint of antibacterial property, it is necessary that the above-mentioned silver ions are contained in the zeolite in an amount of 0.1 to 15% by weight, and the silver ion concentration of less than 0.1% by weight is sufficient. 15% by weight
If it exceeds, it may cause discoloration. The above weight% values are based on the dry standard of zeolite at 110 ° C. Preferably the silver ion is 0.2 to 5% by weight. Silver ion 0.2
~ 5 wt% and copper or zinc ions 0.1 to 16
More preferably, the antibacterial zeolite is contained in a weight percentage. On the other hand, ammonium ion can be contained in the zeolite up to 20% by weight, but the content of ammonium ion in the zeolite is 0.5 to 5% by weight, preferably 0.5 to 2% by weight. It is suitable from the viewpoint of preventing discoloration of.

The amount of the above-mentioned antibacterial zeolite added is 0.0 with respect to 100 parts by weight of the organosilicon compound (A) as the first component.
5 to 20 parts by weight, particularly 0.5 to 10 parts by weight is preferable, and if it is less than 0.05 parts by weight, a satisfactory antibacterial effect may not be obtained, and if it exceeds 20 parts by weight, transparency may be deteriorated. In addition to deterioration, the coating properties at the time of coating, the resulting cured coating, the mechanical strength of the cured molded article may be poor, and the resin composition, cured coating, and molded article may be discolored.

The curable composition having antibacterial and antifungal properties of the present invention is a cured film of the composition (coating thickness: 40-60 μm).
m) has a HAZE value of 30 or less in the total light transmission test,
It is preferably 20 or less, and particularly preferably 10 or less. However, since an organosilicon compound having inorganic properties is excellent in affinity with an inorganic antibacterial zeolite, It is considered that transparency is exhibited. In order to further improve the transparency, the components (A-1) and (A-2) are all organic compounds bonded to a silicon atom except for an alkoxy group, an alkoxyalkoxy group and an acyloxy group in the molecule. The proportion of the phenyl group in the substituent is preferably 5 to 60%, particularly 5 to 50%, in terms of mol. If the content of the phenyl group is too small or too large, the HAZE value may increase.

The curable composition having antibacterial and antifungal properties of the present invention can be cured into a coating film or a molded product by curing in the presence of a curing catalyst or without a catalyst. in this case,
A known catalyst can be used as the curing catalyst, and the curing reaction can be performed by a known method according to this curing agent.

Specifically, when the crosslinking reaction is carried out by a condensation reaction, phosphoric acid, a phosphoric acid ester, organic carboxylates of various metals such as zinc and iron, organic titanic acid esters, aluminum which are known as condensation promoting catalysts. A chelate compound, a lower fatty acid salt of an alkali metal, etc. may be mentioned, and the addition amount thereof is a usual catalytic amount. The conditions for the curing reaction vary depending on the type of curable silicone resin and the condensation-accelerating catalyst to be added, and are generally at room temperature to 300 ° C. for 30 minutes to
It can be selected from the range of 7 days, but particularly when the component (A) is used in the first curable composition,
A room temperature moisture curing type coating composition can be prepared.

Further, when the component (A) has an alkenyl group bonded to a silicon atom, an organohydrogenpolysiloxane containing at least two hydrogen atoms bonded to the silicon atom in one molecule is crosslinked. It may be used as an agent and crosslinked by these addition reactions to be cured. The organohydrogenpolysiloxane used here may be linear, branched, or cyclic, but one having a degree of polymerization of 300 or less is preferable, and the addition amount thereof is in the component (A). Hydrogen atom bonded to silicon atom is 50 to 500 mol% with respect to the alkenyl group.
It is desirable to use it in a ratio such that

A known platinum-based catalyst is preferably added to this addition reaction. Specific examples include chloroplatinic acid, alcohol compounds of chloroplatinic acid, complexes with various olefins, and the like. The amount of the catalyst added is a usual amount of catalyst, and generally, it can be cured at a temperature of 50 to 200 ° C. under a curing condition of several seconds to 3 hours to form a coating film or a molded product.

Further, the curable composition having antibacterial and antifungal properties of the present invention can be used without solvent when the composition is a low-viscosity liquid or when a molded structure is obtained.
When the component (A) is a highly viscous liquid or solid, it is preferable to dilute it with various organic solvents from the viewpoint of viscosity control and workability at the time of coating, and particularly aromatic solvents such as toluene and xylene. Is preferable because it is suitable for industrial production.

The method of mixing the curable composition and the antibacterial zeolite is not particularly limited, and any method can be used as long as a uniform dispersion state of the antibacterial zeolite can be obtained, but the dispersibility is increased. A solution in which the antibacterial zeolite is dispersed in an organic solvent such as isopropyl alcohol may be added to the curable composition for the purpose of shortening the mixing time.

Further, the curable composition having antibacterial and antifungal properties of the present invention contains, in addition to the above-mentioned components, a reinforcing agent such as silica, a polyether-modified silicone compound or a fluorine-based compound within a range not impairing the effects of the present invention. Leveling agent for compounds, etc.,
The addition of a stabilizer such as polycarboxylic acid is optional.

The curable composition having antibacterial and antifungal properties of the present invention is applied to various metal substrates, mortar plates, slate plates, concrete, wood, plastic substrates, glass, etc. by a conventionally known method. It can be cured to form a coating film, or can be molded and cured by a conventionally known method such as cast molding to form a structure. The cured product thus obtained exhibits excellent antibacterial properties, antifungal properties, and antialgal properties, has good transparency, and is safe in terms of environmental hygiene.

[0039]

EXAMPLES The present invention will be specifically described below by showing Examples and Comparative Examples, but the present invention is not limited to the following Examples.

Preparation Example 1 45 parts by weight of partial hydrolysis-condensation product of methyltrimethoxysilane, 35 parts by weight of dimethyldimethoxysilane, 10 parts by weight of diphenyldimethoxysilane, 10 parts of γ-glycidoxypropyltrimethoxysilane.
10 parts by weight of aluminum chelate compound Kelope ACS (trade name, manufactured by Hope Pharmaceutical Co., Ltd.) as a curing catalyst are mixed with stirring at room temperature under a nitrogen atmosphere to prepare active ingredient 1
A curable composition 1 having a concentration of 00% was prepared (phenyl group content in the total organic groups of the silicone resin: 7 mol%).

[Preparation Example 2] In a flask having a volume of 1 L, 300 g of methyltrimethoxysilane, 75 g of phenyltrimethoxysilane, 45 g of dimethyldimethoxysilane, 90 g of diphenyldimethoxysilane, 90 g of γ-glycidoxypropyltrimethoxysilane and 90 g of methanesulfonic acid. Charge 2.9 g and stir at room temperature while stirring 60 g of water
The mixture was added dropwise over 0 minutes, refluxed for 2 hours, and then aged.
Cooled to 0 ° C. Then, 5 g of sodium hydrogen carbonate was added and the mixture was stirred at 30 ° C. for 2 hours for neutralization, and the obtained reaction solution was heated to 100 ° C. under normal pressure to remove by-produced methanol and then filtered. A partially hydrolyzed condensate of the above 5 kinds of silane compounds was obtained. Based on 100 parts by weight of this partially hydrolyzed condensate, TBT-70 as a curing catalyst was used.
5 parts by weight of 0 (butyl titanate) was stirred and mixed at room temperature in a nitrogen atmosphere to prepare a curable composition 2 containing 100% of the active ingredient (phenyl group content in all organic groups of silicone resin: 25 mol%).

Preparation Example 3 A flask having a capacity of 2 L was charged with 279 g of methyltrimethoxysilane, 198 g of phenyltrimethoxysilane, 530 g of xylene and 9.6 g of methanesulfonic acid, and 122 g of water with stirring at 60 ° C.
Was added dropwise over 30 minutes to cause a hydrolytic condensation reaction, and the mixture was further aged for 2 hours at 80 ° C, and then cooled to 30 ° C. Next, 10.1 g of sodium hydrogen carbonate and citric acid 2.
1 g was added, and the mixture was stirred at 30 ° C. for 2 hours. The obtained reaction liquid was distilled at 80 ° C. under normal pressure to remove by-produced methanol, and the residue was washed with water. Next, it was dehydrated with anhydrous sodium sulfate, filtered, and distilled under reduced pressure to obtain a nonvolatile content (silanol group-containing silicone resin: (CH ₃ )).
_0.67 (C ₆ H ₅ ) _0.33 Si (OH) _0.16 (OCH ₃ ) _0.04
A xylene solution having an O _1.4 ) content of 60% by weight was obtained.
This silanol group-containing silicone resin xylene solution 1
3 parts by weight of zinc octylate as a curing catalyst for 100 parts by weight
By mixing the parts by weight with stirring at room temperature under a nitrogen atmosphere, a curable composition 3 containing 60% of the active ingredient was prepared (phenyl group content in all organic groups of silicone resin: 33 mol%).

[Example 1] 20 parts by weight of Zeomic AW10N powder (trade name, manufactured by Sinanen Zeomic Co., Ltd.) as an antibacterial zeolite was mixed with isopropyl alcohol (IP).
A) 20% IPA of Zeomic when mixed with 80 parts by weight
A dispersion was prepared. 5 parts by weight of Zeomic 20% IPA dispersion was mixed with 100 parts by weight of the curable composition 1 to obtain a Zeomic addition curable composition (the amount of Zeomic powder added to the curable composition = 1 phr). . Width 5c
m × length 10 cm × thickness 2 mm, on one surface of a glass plate, the Zeomic addition curable composition prepared as described above was applied so that the film thickness when cured was 50 μm,
It was left to cure for 3 days in an atmosphere of 25 ° C. and 65% relative humidity. The obtained cured coating was tested for antibacterial properties and coating physical properties (HAZE value, pencil hardness, adhesiveness, solvent resistance), and the results shown in Table 1 were obtained.

[Examples 2 to 5] The same treatment as in Example 1 was carried out except that the type of the curable composition used and the addition amount of the Zeomic powder were changed as shown in Table 1. Antibacterial and coating physical properties (HAZE value, pencil hardness,
When the adhesion and solvent resistance) were tested, the results shown in Table 1 were obtained. When the curable composition 3 was used, it was air-dried at room temperature for 10 minutes and then heated at 200 ° C. for 60 minutes to obtain a cured film.

[Comparative Examples 1 to 3] With respect to the curable compositions 1 to 3, the 20% IPA dispersion of Zeomic was not added, and I
Example 1 except that only PA was compounded at a ratio of 5 phr
~ 5 to prepare a curable composition without the addition of Zeomic, the antibacterial properties and coating physical properties of the cured coating obtained by the same treatment (Haze value, pencil hardness, adhesion, solvent resistance) Was tested and the results shown in Table 1 were obtained.

[Comparative Example 4] With respect to 100 parts by weight of the curable composition 2, 44 parts by weight of 50% IPA dispersion of Zeomic was added (the amount of the Zeomic powder added to the curable composition was 22 phr). The same treatment as in Example 1 was carried out to prepare a Zeomic-added curable composition, and the cured film obtained by the same treatment was subjected to the same antibacterial properties and physical properties (HAZE value,
Pencil hardness, adhesion, solvent resistance) were tested and Table 1
The results shown in are obtained.

The antibacterial properties and the physical properties of the film were measured by the following methods. Antibacterial property: 0.4 ml of a suspension of the bacteria prepared in 1/500 normal broth medium was dropped on each cured film, and a sterilized polyethylene film was placed on it and stored at 35 ° C. for 24 hours. After storage, sterilized SCDLP liquid medium 10m
The bacteria on the surface of each cured coating were washed out with 1. The number of surviving bacteria in the washed-out liquid was measured by the pour plate method using an agar medium for measuring the number of bacteria. As a control, a test using only the bacterial solution was also performed at the same time. Staphylococcus aureus: IFO12732 Escherichia coli: IFO3972 Haze value: turbidity, using a haze meter NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd., light source: halogen lamp), according to the total light transmittance test method JIS K 7361,
The above glass plate alone was measured as a standard sample (HAZE value = 0). Pencil hardness: Pencil scratch value by hand-drawing method Adhesion: By the cross-cut tape method, how the film peeled off was visually determined as follows. ◯ = No peeling at all △ = Partial peeling × = Whole surface peeling Solvent resistance: ○ When xylene rubbing was 100 times without elution or scratch of the coating, and when less than 100 times, dissolution or scratching of the coating occurred. The thing was marked as x.

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[Table 1]

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INDUSTRIAL APPLICABILITY According to the present invention, a curable composition which exhibits excellent antibacterial properties, fungicidal properties and algaeproof properties for a long period of time without impairing the original properties of the curable organosilicon compound is obtained. The obtained cured product has excellent transparency, does not discolor even when heated, and has antibacterial and antifungal properties that can be safely used in terms of environment and hygiene.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Masaaki Yamatani             Gunma Prefecture Usui District, Matsuida Town             Shin-Etsu Chemical Co., Ltd. Silicone electronic materials             Inside the technical laboratory (72) Inventor Masahiro Yoshizawa             Gunma Prefecture Usui District, Matsuida Town             Shin-Etsu Chemical Co., Ltd. Silicone electronic materials             Inside the technical laboratory F-term (reference) 4J002 CP031 CP061 CP081 CP091                       CP101 DA077 DH028 DJ006                       EG008 EW048 EZ008 FD148                       FD186 FD187 GH00 GL00

Claims (5)

[Claims] 1. An antibacterial zeolite 0.05 to 20 parts by weight containing (A) 100 parts by weight of a curable organosilicon compound selected from a silane compound and a silicone resin, and (B) 0.1 to 15% by weight of silver ion. A curable composition having antibacterial and antifungal properties, characterized in that the HAZE value of a cured coating having a coating thickness of 40 to 60 μm in a total light transmission test is 30 or less. 2. The curable organosilicon compound as the component (A) is
(A-1) The following general formula (1) R ¹ _a Si (OR ² ) _4-a (1) (In the formula, R ¹ may be the same or different and may be a substituted or unsubstituted monovalent hydrocarbon group, R ² represents an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group or an acyl group, and a is any number of 0, 1 and 2, or a partial hydrolysis thereof. The curable composition according to claim 1, which comprises one or a mixture of two or more condensates. 3. The organosilicon compound as the component (A) is (A-
2) The following general formula (2) R ¹ _a SiX _4-a (2) (In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different, and a is 0, 1 or 2 Or X is an OR ² group or a halogen atom, and R ² is an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group or an acyl group) or a partial hydrolysis thereof. The following general formula (3) R ¹ _b Si (OH) _c (OR ² ) _d O _{(4-bcd) / 2} (3) (in the formula) obtained by hydrolytically condensing one or more condensates , R ¹ and R ² are the same as above, and b, c and d
Is 0.2 ≦ b ≦ 1.8, 0 <c ≦ 0.5, 0 ≦ d ≦
It is a number that satisfies 0.5 and 0.5 ≦ b + c + d ≦ 2.5. The curable composition according to claim 1, which comprises one or a mixture of two or more silanol group-containing silicone resins represented by the formula (1). 4. The ratio of the phenyl group to the curable organosilicon compound in the total organic substituents bonded to silicon atoms excluding alkoxy groups, alkoxyalkoxy groups, and acyloxy groups in the molecule is 5 to mol. 60% is the curable composition having antibacterial and antifungal properties according to claim 2 or 3. 5. A cured product obtained by curing the curable composition having antibacterial and antifungal properties according to any one of claims 1 to 4.