JPH11314955A - Antibacterial artificial marble - Google Patents

Abstract

(57) [Problem] An antibacterial artificial marble mainly composed of a thermosetting resin, which exhibits extremely little discoloration over time during processing, storage and use, and exhibits a stable antibacterial effect. provide. A ZnO 50 to 80 mole%, B ₂ O ₃ and / or P ₂ O ₅ containing 20 to 50 mol%, the effective glass content of alkali metal oxides is 0-1 mol% An antibacterial artificial marble comprising an antibacterial agent and a thermosetting resin as components.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial artificial marble used for kitchen counters, sinks, toilet articles, bath articles and the like. More specifically, in an artificial marble mainly composed of a thermosetting resin, there is extremely little discoloration over time during processing, storage and use, and an antibacterial artificial marble imparted with an antibacterial property showing a stable antibacterial effect. About.

[0002]

2. Description of the Related Art Artificial marble has been widely used for kitchen counters, wash basins, toilet articles, bath articles, etc. because of its excellent heat resistance, water resistance, wear resistance and the like. Most of these uses are used around water, so that bacteria and molds are easily propagated. Particularly in hospitals, schools, public facilities, etc. used by unspecified number of people, hospital-acquired methicillin-resistant Staphylococcus aureus (MRSA), Escherichia coli O-1
Therefore, artificial marble has been strongly antibacterial.

[0003] In order to solve these problems, attempts have been made to add an antibacterial agent to artificial marble or to apply it to a surface layer. Antibacterial agents can be roughly classified into organic antibacterial agents and inorganic antibacterial agents, but the former has questions about safety, corrosiveness, and sustainability of antibacterial effects. On the other hand, inorganic antibacterial agents are excellent in safety, corrosiveness and persistence of effects. However, most of inorganic antibacterial agents contain silver having antibacterial effect,
There is a problem that discoloration occurs over time during processing, storage, or use.

Since artificial marble is frequently exposed to water, hot water, various foodstuffs, various cleaning agents, heat, and the like, discoloration is very likely to occur. In order to prevent discoloration, there is a method of using an antibacterial agent in which silver ions are supported on a specific carrier, but discoloration cannot be sufficiently suppressed as long as silver is present. Further, a method of microencapsulating the antibacterial agent itself has been proposed, but there is a problem that the antibacterial effect is reduced.

As an antibacterial agent containing no silver, JP-A-7-257938 has proposed a glass for an antibacterial agent containing zinc. Since the antibacterial glass exhibits an antibacterial effect due to the eluted zinc, the antibacterial effect is high in the initial stage, but the antibacterial effect is not sufficiently maintained. Further, since the water resistance is low, there is a problem that artificial marble to which this is added is whitened by warm water.

[0006]

SUMMARY OF THE INVENTION The present invention relates to an artificial marble mainly composed of a thermosetting resin used for kitchen counters, wash basins, toilet articles, bath articles, etc., which is used for processing, storage and use over time. It is an object of the present invention to provide an antibacterial artificial marble which shows extremely little discoloration and a stable antibacterial effect.

[0007]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and have found that ZnO is contained at a very high concentration and the content ratio of the alkali metal oxide is extremely low. The present inventors have found that an artificial marble in which a specific glassy antibacterial agent is contained in a thermosetting resin is an excellent one that has solved the above problems, and has completed the present invention. That is, the present invention is 50 to 80 mol% of ZnO, B ₂
O ₃ and / or P ₂ O ₅ containing 20 to 50 mol%,
An antibacterial artificial marble comprising an antibacterial agent and a thermosetting resin containing glass having an alkali metal oxide content of 0 to 1 mol% as an active ingredient.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. ○ antimicrobial antimicrobials in the present invention (hereinafter, abbreviated as vitreous antimicrobial agent), 50 to 80 mol% of ZnO, B ₂ O ₃ and /
Or P ₂ O ₅ containing 20 to 50 mol%, the content of alkali metal oxides is as an active ingredient a glass 0-1 mol%.

The preferred ZnO content is 55-75.
Mol%, more preferably 60 to 70 mol%. If ZnO is added in an amount of more than 80 mol%, there is a problem that it is difficult to vitrify stably, and if it is less than 50 mol%, the antibacterial properties of the glass of the present invention become insufficient.

A preferable content ratio of B ₂ O ₃ and / or P ₂ O ₅ is 25 to 45 mol%, more preferably 3 to 45 mol%.
0 to 40 mol%. If B ₂ O ₃ and / or P ₂ O ₅ is added in an amount of more than 50 mol%, the water solubility of the glass of the present invention increases, and the excellent antibacterial properties and discoloration resistance of the glass of the present invention are impaired. There is a problem that
If it is less than 20 mol%, there is a problem that it is difficult to stabilize the glass. The blend of B ₂ O ₃ and P ₂ O ₅ may be both or only one of them.

In the vitreous antibacterial agent of the present invention,
The content ratio of the alkali metal oxide is 0 to 1 mol%,
This means that the artificial marble of the present invention has excellent antibacterial properties,
It is extremely important for exhibiting discoloration resistance. That is, when the content of the alkali metal oxide is more than 1 mol%,
The water solubility of the vitreous antibacterial agent of the present invention becomes extremely large, and the sustained antibacterial property and discoloration resistance of the artificial marble of the present invention are impaired.

The essential glass-forming components in the present invention are:
B ₂ O ₃ or is a P ₂ O _5, it is possible to add other glass forming ingredients as desired. Preferred examples of other glass-forming components include SiO ₂ , Al ₂ O ₃ , and Ti.
O ₂ , ZrO _{2 and the} like. The preferable content ratio of other glass-forming components is 20 mol% or less, more preferably 15 mol% or less.

If desired, MgO, CaO and Ca
F _{2 and the} like can be appropriately contained. These so-called “modifying components” are effective in facilitating melting and moldability of the glass, but when contained in a large amount, the water resistance of the glass may be reduced, so that at most 3 mol% or less. And more preferably 1 mol% or less.

The method for producing the vitreous antibacterial agent in the present invention is not limited, and a known production method can be employed. Generally, the raw material mixture of glass is 1000-200 in a melting pot.
After melting at 0 ° C., the melt is quenched to prepare a glass, and then the obtained lump glass is ground to easily obtain a powdery glass.

The glass, which is an active ingredient of the vitreous antibacterial agent of the present invention, has a zinc oxide (melting point: about 2000 ° C.) concentration of the conventional antibacterial agent in order to exhibit a much superior antibacterial property as compared with the conventional one. It may be considered difficult to vitrify because it is expensive compared to prescription glass, but this is overlooked. Zinc oxide itself has the ability to form a network of glass, so if it is melted at an appropriate melting temperature and quenching means suitable for the cooling characteristics of the melt is used, glass having any composition in the present invention can be obtained. Can be easily obtained.

In order to enhance the quenching effect, it is effective to increase the contact area between the molten material and the cooling body. For example, the molten material of glass is sandwiched between two rotating metal rollers cooled by a coolant such as water. Is passed through at a high speed to obtain an extremely large cooling effect. By using this cooling method, vitrification is extremely easy. Further, when cooled by this method, since the glass that has come out between the rollers is formed into a thin plate, it can be very easily crushed into a powder.

(4) Antibacterial agent of tetravalent metal phosphate When the vitreous antibacterial agent of the present invention is used in combination with the antibacterial agent of tetravalent metal phosphate, its antibacterial property can be further enhanced. This is because a synergistic effect is obtained by two different antibacterial components of zinc ions in glass and antibacterial metal ions in the tetravalent metal phosphate antibacterial agent.

Further, the vitreous antibacterial agent in the present invention comprises:
Since the anti-discoloration effect is extremely excellent, the coloring and discoloration of the resin product will not occur when a tetravalent metal phosphate antibacterial agent is used in combination. The tetravalent metal phosphate antibacterial agent in the present invention is represented by the following general formula [1]. M ¹ aAb M ² c (PO ₄ ) _d · nH ₂ O [1] (M ¹ is silver, copper, zinc, tin, mercury, lead, iron, cobalt,
At least one l-valent (l is a positive integer) metal ion selected from nickel, manganese, arsenic, antimony, bismuth, barium, cadmium, and chromium, and A is an alkali metal ion, an alkaline earth metal ion, or ammonium At least one selected from ions and hydrogen ions
A species of m-valent (m is a positive integer) ion, M ² is a tetravalent metal ion, n is a number satisfying 0 ≦ n ≦ 6,
a and b are both la + mb = 1 or la + mb = 2
Where c and d are la + mb = 1,
c = 2, d = 3, and when la + mb = 2, c = 1, d
= 2. )

The compound represented by the general formula [1] is a crystalline compound or an amorphous compound having a layered structure or a three-dimensional knitted structure belonging to the space group R3C. As the tetravalent metal phosphate antibacterial agent in the present invention, a crystalline compound having a three-dimensional network structure is preferable because there is little change in physical properties. M ¹ in the above general formula [1] is known as a metal having antifungal, antibacterial and antialgal properties, and among these, silver is not only safe but also antifungal and antibacterial. It is particularly effective as a metal capable of enhancing algal resistance.

A in the general formula [1] is at least one ion selected from the group consisting of an alkali metal ion, an alkaline earth metal ion, an ammonium ion and a hydrogen ion. Preferred examples thereof include lithium, sodium and potassium. And alkaline earth metal ions such as magnesium and calcium or hydrogen ions. Among these, potassium, sodium and hydrogen ions are preferred ions in view of the stability of the compound and availability at low cost.

M ² in the general formula [1] is a tetravalent metal ion, and preferred specific examples thereof include zirconium,
There are titanium and tin, and considering the safety of the compound, zirconium and titanium are particularly preferred tetravalent metal ions.

In order to exhibit the fungicidal, antibacterial and algicidal properties, the larger the value of a in the general formula [1], the better.
When the value of a is 0.001 or more, it is possible to sufficiently exhibit fungicide, antibacterial properties and antialgal properties. However, if the value of a is less than 0.001, it may be difficult to exhibit the fungicide, antibacterial properties and anti-algal properties for a long time, so the value of a is set to 0.01 or more. Is preferred.
Further, in order to obtain an effect by adding a small amount, the value of a is 0.1
It is more preferable to make the above.

Preferred specific examples of the antibacterial agent represented by the general formula [1] are as follows. Ag _0.001 Li _1.999 Zr (PO ₄ ) ₂ Ag _0.01 Na _1.99 Zr (PO ₄ ) ₂ Ag _0.01 K _1.99 Sn (PO ₄ ) _{2 1.2} H ₂ O Ag _0.1 (NH ₄ ) _1.9 Ti (PO ₄ ) _2. Ag in each of the above formulas was changed to Z while maintaining the same charge as the charge of silver ions per mole of 4H ₂ O and compound.
It is a compound substituted with n, Mn, Ni, Pb, Hg, Sn, or Cu. The following antibacterial agents are also preferable. Ag _0.005 Li _0.995 Zr ₂ (PO ₄ ) ₃ Ag _0.01 (NH ₄ ) _0.99 Zr ₂ (PO ₄ ) ₃ Ag _0.05 Na _0.95 Zr ₂ (PO ₄ ) ₃ Ag _0.2 K _0.8 Ti ₂ (PO ₄ ) ₃ Ag _0.1 H _0.9 Zr ₂ (PO ₄ ) ₃ Ag _0.40 H _0.15 Na _0.45 Zr ₂ (PO ₄ ) ₃ Ag _0.60 H _0.10 Na _0.30 Zr ₂ (PO ₄ ) ₃ and the same charge amount as silver ion per mole of compound In each of the above equations, Ag is changed to Z
Compounds substituted with n, Mn, Ni, Pb, Hg, Sn, or Cu.

[0024] The tetravalent metal phosphate antibacterial agent of the present invention is obtained by supporting an antibacterial metal ion on a phosphate compound. There are a wet method, a hydrothermal method and the like, which can be easily obtained by a known production method.

The method for supporting the antibacterial metal ion on the tetravalent metal phosphate compound is not particularly limited. However, a method of supporting by an ion exchange reaction is generally used.

The blending ratio of the glassy antibacterial agent and the tetravalent metal phosphate antibacterial agent The preferred blending ratio of the tetravalent metal phosphate antibacterial agent in the present invention is the total weight of the glassy antibacterial agent and the present invention. The amount is from 0 to 70 parts, more preferably from 0 to 50 parts, per 100 parts by weight (hereinafter abbreviated as "part"). Even if the amount is more than 70 parts, it is not possible to expect a great improvement in the combined effect with the vitreous antibacterial agent. On the other hand, when added to the resin, discoloration due to the tetravalent metal phosphate antibacterial agent may occur.

In addition, the antibacterial artificial marble of the present invention contains, in addition to a vitreous antibacterial agent or an antibacterial agent composition containing a tetravalent metal phosphate-based antibacterial agent added thereto, to improve other physical properties. Various other additives can be mixed as needed. Specific examples include antioxidants, light stabilizers, antistatic agents, and impact modifiers.

Method for Preparing Antibacterial Agent Composition The method for mixing the vitreous antibacterial agent and the tetravalent metal phosphate antibacterial agent in the present invention is not particularly limited. For example, mixing using a Henschel mixer may be mentioned, and the mixing conditions may be appropriately adjusted only by the rotation speed (800 to 3000 rpm) and the mixing time (several minutes to several tens of minutes) depending on the mixing amount. It can be done with pressure.

Thermosetting Resin The antibacterial artificial marble of the present invention includes those in which an antibacterial agent is contained in the entire artificial marble and those in which a gelcoat layer constituting the surface of the artificial marble contains an antibacterial agent. In both cases with and without the gel coat layer, the artificial marble substrate and the gel coat layer are made of a thermosetting resin.

The thermosetting resin used in the present invention is not particularly limited as long as it is a resin capable of being cured to form an artificial marble base material or a gel coat layer. Examples thereof include an isophthalic unsaturated polyester and a terephthalic unsaturated polyester. Polymers such as polyester, epoxy (meth) acrylate, melamine acrylate, melamine (meth) acrylate, (meth) acrylate, methyl (meth) acrylate,
There are oligomers and those containing at least one polymerizable monomer forming these polymers as a main component.

If necessary, a crosslinking agent, a curing agent, a curing accelerator, a coloring agent, and the like can be added. Examples of the crosslinking agent include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate. Examples of the curing agent include tertiary butyl peroxymaleic acid, benzoyl peroxide, and methyl etoketone peroxide. Examples of the curing accelerator include cobalt naphthenate.

Any known method can be used to mix the glassy antibacterial agent or the antibacterial agent composition containing the same with the tetravalent metal phosphate antibacterial agent in the composition for artificial marble. For example, a predetermined amount of a vitreous antibacterial agent or an antibacterial agent composition may be added to the composition for artificial marble, and kneaded and mixed with a kneader, mixer, roll mill, extruder, or the like. A preferred compounding ratio of the vitreous antibacterial agent or the antibacterial agent composition in the artificial marble or gel coat layer is 0.05 to 10 parts, more preferably 0.5 to 5 parts, per 100 parts of the artificial marble or gel coat layer. If the amount is less than 0.05 part, the antibacterial property of the artificial marble may be insufficient.
Even if it is more than 0 parts, there is almost no improvement in the antibacterial effect.

Method for Producing Antibacterial Artificial Marble Antibacterial artificial marble is produced as follows. A thermosetting resin, a curing catalyst, a glassy antibacterial agent, or an antibacterial agent composition containing the same and a tetravalent metal phosphate-based antibacterial agent are mixed. If necessary, an inorganic filler such as glass fiber or aluminum hydroxide, a crosslinking agent, a curing accelerator, a pigment and the like may be added and mixed. The mixture is poured into a mold and cured at room temperature or by heating to obtain an artificial marble.
In addition to injection molding, other molding methods such as injection molding and press molding can be used, but injection molding is most preferable.

In the case of artificial marble having a gel coat layer on the surface of the base resin, it is generally prepared as follows. A coating composition for preparing a gel coat layer is applied to a molding die and cured by a spray-up method or the like. Next, the composition for base resin is poured into a mold and cured. By removing the laminate of the gel coat layer and the base resin, an artificial marble can be obtained.

[0035]

The mechanism by which the vitreous antibacterial agent of the present invention has excellent antibacterial properties and discoloration resistance is presumed as follows. That is, since the vitreous antibacterial agent of the present invention contains a high concentration of ZnO and has a very low alkali metal content, it has extremely low water solubility and, first, is excellent in water resistance. Since the surface layer of the glass constituting the vitreous antibacterial agent has a low elution of Zn, the glass surface layer always has a high concentration of Zn, and the antibacterial property of Zn can be maintained for a long time. In addition, since the water solubility of the vitreous antibacterial agent is small, elution of Zn ions and alkali metal ions, which cause discoloration, is small, and the discoloration resistance is excellent. When the above glassy antibacterial agent and the tetravalent metal phosphate-based antibacterial agent used in this patent are used in combination, the antibacterial property is improved as compared with the case where each is used alone. It is presumed that a synergistic effect of the antibacterial agent is exhibited.

[0036]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. Synthesis Example 1 (tetravalent metal phosphate antibacterial agent) A precipitate was formed by mixing an aqueous solution of zirconium sulfate and an aqueous solution of phosphoric acid so that the ratio of zirconium to phosphorus was 2: 3, and sodium hydroxide was used. After adjusting the pH to 2 using an aqueous solution of 130 ° C. under hydrothermal conditions,
By heating for 12 hours, crystalline zirconium phosphate [NaZr ₂ (PO ₄ ) ₃ ] was obtained. The phosphate compound obtained above was thoroughly washed with water, added to silver nitrate and a 1N aqueous solution of nitric acid, stirred at 60 ° C. for 4 hours, thoroughly washed with water, and dried. After firing this at 750 ° C. for 4 hours in a firing furnace,
Silver based inorganic antibacterial agent Ag _0.50 Na ₀ by grinding. ₂₃ H
_0. To give the _{27 Zr 2 (PO 4) 3} . The obtained silver-based inorganic antibacterial agent is a white powder having an average particle size of 0.92 μm.

Synthesis Example 2 (Preparation of zeolite-based antibacterial agent) The content of silver was changed in the same manner as in Reference Example 1 except that commercially available zeolite 4A was used instead of the crystalline zirconium phosphate synthesized in Synthesis Example 1. Was 4% by weight.

Reference Example 1 (Preparation of vitreous antibacterial agent) A raw material mixture having the composition shown in Samples No. 1 to No. 3 in Table 1 was melted at 1000 to 1400 ° C. to produce a glass. The glass was wet-pulverized with a ball mill to obtain a glassy antibacterial agent having an average particle size of about 10 μm.

Comparative Reference Example 1 (Preparation of vitreous antibacterial agent) The average particle diameter was approximately the same as in Reference Example 1 except that the raw material preparations having the compositions shown in Samples Nos. 4 to 6 in Table 1 were used. A 10 μm glassy antimicrobial agent was obtained.

Reference Example 2 (Preparation of Antibacterial Agent Composition) The tetravalent metal phosphate-based antibacterial agent prepared in Synthesis Example 1 and the vitreous antibacterial agent sample No. 1 or 3 were prepared at the ratios shown in Table 2. The antibacterial agent composition (Sample No. 7 to Sample No. 1)
0) was obtained.

[0041]

[Table 1]

[0042]

[Table 2]

Example 1 150 parts of aluminum hydroxide was added to 100 parts of polymethyl methacrylate / methyl methacrylate, and a curing agent and a curing accelerator were added to 100 parts of the artificial marble resin composition. 1.0 part of various glassy antibacterial agents (Sample Nos. 1 to 3) or antibacterial agent compositions (Samples Nos. 7 to 10) prepared in Reference Examples 1 and 2 were added,
Mixed. This composition was poured into a mold, cured at room temperature, and demolded to obtain an antibacterial artificial marble (prototype No. 1).
No. 3 and prototype Nos. 7 to 10. However, the artificial marble of prototype No. K was prepared using the glassy antibacterial agent, antibacterial agent composition or antibacterial agent of sample No. K (K is a positive integer). Hereinafter, it is similarly indicated in Comparative Example 1).

Comparative Example 1 Example 1 was repeated except that the vitreous antibacterial agents of Samples Nos. 4 to 6 prepared in Reference Example 2 were used instead of the vitreous antibacterial agent or the antibacterial agent composition in Example 1. Antibacterial artificial marble was obtained in the same manner as described above (prototypes No. 4 to No. 6).

Comparative Example 2 An antibacterial artificial marble was obtained in the same manner as in Example 1 except that the antibacterial agent prepared in Synthesis Example 1 was used instead of the vitreous antibacterial agent or the antibacterial agent composition in Example 1. (Prototype No.1
1).

Comparative Example 3 An antibacterial artificial marble was obtained in the same manner as in Example 1, except that the antibacterial agent prepared in Synthesis Example 2 was used instead of the vitreous antibacterial agent or the antibacterial agent composition in Example 1. (Prototype No.1
2).

Comparative Example 4 An artificial marble was obtained in the same manner as in Example 1 except that no antibacterial agent was added (prototype No. 13).

Evaluation Test 1 The color of the antibacterial artificial marble prepared in Example 1 and Comparative Examples 1 to 4 was visually checked for discoloration evaluation. Further, the antibacterial activity of the produced molded body was evaluated by the following method. Escherichia coli is used as the test bacterium, and antibacterial artificial marble
The plate was cut into a plate of cm × 5 cm × 2 mm, and 0.5 ml of a bacterial solution was dropped on the surface so that the number of bacteria per one plate surface was 10 ⁵ to 10 ⁶ . 4.5cm from above
A 4.5 cm polyethylene film is placed on the surface, and the bacterial solution is uniformly contacted with the surface.
Stored for 4 hours. Immediately after the start of storage (the number of theoretically added bacteria) and 2
After storage for 4 hours, the surviving bacteria on the plate are washed out with a culture medium for cell count (SCDLP liquid medium), and the washed liquid is subjected to a pour plate culture method (37 ° C. 2
Days), the number of viable bacteria was measured, and 5 cm × 5
It was converted to the number of viable bacteria per cm. The initial number of bacteria was 1.4.
× 10 ⁵ , and the number of bacteria of a control which was subjected to the same operation without using the sample was 9.5 × 10 ⁶ . Further, the color and the antibacterial activity after immersing the plate in hot water of 80 ° C. for 500 hours were evaluated, and the results are shown in Table 3.

[0049]

[Table 3]

Antibacterial artificial marble containing the vitreous antibacterial agent or antibacterial agent composition of the present invention (prototype Nos. 1 to 3)
Nos. 3, and 7 to 10) were confirmed to have excellent antibacterial properties, discoloration resistance, and warm water resistance. On the other hand, Z
Although the content ratio of nO is large, the plate (prototype No. 4) containing the vitreous antibacterial agent in which the content ratio of alkali metal oxide is larger than 1 mol% is inferior in discoloration resistance and the mixing molar ratio of ZnO is small. The plate containing the antimicrobial glass (prototype No. 5) was inferior in antimicrobial properties. In addition, a plate containing silver together with zinc in glass (prototype No.
6) resulted in poor discoloration resistance.

Example 2 Various vitreous antibacterial agents prepared in Reference Example 1 (sample N) were added to 100 parts of an isophthalic acid-based unsaturated polyester resin.
o.1 to No.3) or an antibacterial agent composition (Sample Nos. 7-1)
1.0) was added and mixed. Predetermined amounts of methyl etoketone peroxide as a curing agent and cobalt naphthenate as a curing accelerator were added to obtain a coating composition for preparing a gel coat layer. Apply the paint composition to the inside of the mold with a spray gun so that the thickness is about 0.5 mm,
Cured at room temperature. Then add 50 parts of aluminum hydroxide
An artificial marble molded product was obtained by injecting a base resin composition containing an isophthalic acid-based unsaturated polyester resin as a main component containing the same by weight into a mold, and curing and demolding at room temperature (Prototype Nos. G1 to No. .G3, Prototype No.G7 to G10, but Prototype N
The o.GK artificial marble was prepared using the glassy antibacterial agent, antibacterial agent composition or antibacterial agent of Sample No. K (K is a positive integer). Hereinafter, it is similarly indicated in Comparative Example 5).

Comparative Example 5 An antibacterial artificial marble was obtained in the same manner as in Example 2, except that the antibacterial agent prepared in Synthesis Example 1 was used instead of the vitreous antibacterial agent or the antibacterial agent composition in Example 2. (Prototype No.G1
1).

Comparative Example 6 An antibacterial artificial marble was obtained in the same manner as in Example 2 except that the antibacterial agent prepared in Synthesis Example 2 was used instead of the vitreous antibacterial agent or the antibacterial agent composition in Example 2. (Prototype No.G1
2).

Comparative Example 7 An artificial marble was obtained in the same manner as in Example 2 except that no antibacterial agent was added (prototype No. G13).

Evaluation Test 2 The antibacterial artificial marble prepared in Example 2 and Comparative Examples 5 to 7 was prepared in the same manner as in the method performed on the antibacterial artificial marble prepared in Example 1 and Comparative Examples 1 to 4. , Antibacterial properties, discoloration resistance and warm water resistance were evaluated.

[0056]

[Table 4]

Antibacterial artificial marble containing the glassy antibacterial agent or the antibacterial agent composition of the present invention (prototype Nos. G1 to G
3, and G7 to G10) were confirmed to have excellent antibacterial properties, resistance to discoloration, and excellent resistance to warm water. on the other hand,
Although the content of ZnO is large, the antibacterial plate (prototype No. G4) containing the glass for antibacterial agents containing alkali metal oxides having a content of more than 1 mol% is inferior in discoloration resistance.
The antibacterial plate (prototype No. G5) containing the antimicrobial agent glass having a small molar ratio of nO was inferior in antibacterial properties. Further, the antibacterial plate containing silver together with zinc in the glass (prototype No. G6) resulted in poor discoloration resistance.

[0058]

The antibacterial artificial marble of the present invention is obtained by
Very little discoloration over time during storage and use, and has excellent antibacterial properties showing stable antibacterial effects. Further, the antibacterial artificial marble of the present invention also has warm water resistance and discoloration resistance, and is extremely useful as an artificial marble used for kitchen counters, wash basins, toilet articles, bath articles and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // (C04B 26/02 14:22)

Claims (2)

[Claims] 1. A glass containing 50 to 80 mol% of ZnO, 20 to 50 mol% of B ₂ O ₃ and / or P ₂ O _5, and containing 0 to 1 mol% of an alkali metal oxide. An antibacterial artificial marble comprising an antibacterial agent as an active ingredient and a thermosetting resin. 2. An artificial marble having a gel coat layer on the surface of a base resin, wherein the gel coat layer comprises the antibacterial agent according to claim 1 and a thermosetting resin.