JP3479581B2 - Anti-MRSA artificial marble having two-layer structure and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to MRSA (Methicillin Resistant Staphylococcus aureus).
The present invention relates to an artificial marble having a two-layer structure having an antibacterial property against phylococcus Aureus) and a method for producing the artificial marble.

[0002]

2. Description of the Related Art Artificial marble has excellent properties such as texture, workability, workability, weather resistance and strength.
For example, it is widely used in many applications such as counter tops, kitchen tops, furniture, sanitary applications, interior materials, and stationary accessories. Further, from the viewpoint of the cleanliness provided by artificial marble, it has been used in hospitals and nursing homes in recent years. This artificial marble is generally composed of a resin, an inorganic filler, a catalyst, a cross-linking agent, and a pigment, and has a unique graceful appearance, easy workability, and excellent strength.

[0003]

[Problems to be Solved by the Invention] In recent years, with the diversification of lifestyles of Japanese people, clean consciousness has spread among young people, mainly among young people. In addition, nosocomial infections and secondary infections in hospitals have become a problem. Under such circumstances, there is a demand for the development of a clean material or a material that does not propagate bacteria. On the other hand, since artificial marble is non-porous, it has been popular as a clean material because it is less prone to bacterial growth than other porous building materials and is easy to wash. In the field of general resin materials, there are some conventional techniques for imparting antibacterial, antifungal, and deodorant functions to resin materials (Japanese Patent Laid-Open No. 5-295127).
JP-A-5-140331, JP-A-5-25319,
JP-A-2-124949 and JP-A-4-93360). However, among the antibacterial functions, MRS, which has a particular problem
There was almost no technology that paid attention to A and examined what kind of structure should be adopted to give anti-MRSA property to the resin material.

The present invention has been made in view of the above prior art, and an object of the present invention is to provide an artificial marble having an anti-MRSA property and a method for producing the artificial marble.

[0005]

The inventors of the present invention have found that anti-MRS
As a result of intensive studies based on the new viewpoint of providing A-type artificial marble, when aluminum hydroxide as an inorganic filler of artificial marble and an antibacterial agent containing zinc oxide are used together, both components are unexpected. It was found that the above-mentioned effect was exerted and that a very good anti-MRSA property was given, and the present invention was completed.

That is, according to the present invention, the resin component (a) 90-
10 parts by weight, 10 to 90 parts by weight of aluminum hydroxide (b), and an antibacterial agent (c) containing zinc oxide with respect to 100 parts by weight of the resin component and aluminum hydroxide in total.
A thin layer formed from the composition (M1) containing 0.1 to 10.0 parts by weight, 90 to 10 parts by weight of the resin component (a) and 10 to 90 parts by weight of aluminum hydroxide (b), An anti-MRSA artificial marble having a two-layer structure with a resin layer formed from a composition (M2) containing no antibacterial agent (c).

The present invention also provides a method for producing an anti-MRSA artificial marble, which comprises the steps of forming a thin layer from the composition (M1) and then forming a resin layer from the composition (M2) in a mold; , In the mold, the composition (M
A method for producing an anti-MRSA artificial marble, which comprises the step of forming a resin layer according to 2) and then forming a thinner layer than the composition (M1).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the present invention will be described in detail below.

As the resin component (a) used in the present invention,
The resin is not particularly limited as long as it is a resin that can be cured to form an artificial marble, and various monomers conventionally known as a resin component for artificial marble, a mixture of a monomer and a polymer, and the like can be appropriately used. For example, when producing an acrylic artificial marble or an unsaturated polyester artificial marble, various (meth) acrylic monomers or unsaturated polyesters may be used. In particular, it is desirable to form the resin component (a) by using at least one selected from the group consisting of melamine (meth) acrylate, glycidyl (meth) acrylate, methyl (meth) acrylate and unsaturated polyester. In addition, in this specification, "(meth) acrylic" means "acrylic and / or methacrylic".

Specific examples of the (meth) acrylic monomer used in the resin component (a) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
(Meth) acrylic acid ester such as benzyl (meth) acrylate; glycidyl (meth) acrylate; melamine (meth) acrylate and the like. If necessary, a vinyl monomer for copolymerization may be used together with the (meth) acrylic monomer. As this vinyl monomer for copolymerization,
Examples thereof include styrene, α-methylstyrene, vinyltoluene, acrylonitrile, vinyl acetate and the like. The amount of the vinyl monomer for copolymerization used is preferably 10 parts by weight or less per 100 parts by weight of the monomer used.

Further, as a cross-linking agent for cross-linking the resin component (a), ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth). Acrylate, 1,6-
Having multiple polymerizable double bonds in the molecule such as hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polybutylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, etc. It is desirable to use a crosslinkable vinyl monomer together. Of these, ethylene glycol di (meth) acrylate is particularly preferable. The amount of the crosslinkable vinyl monomer used is usually 0.05 to 20 parts by weight.

When an acrylic monomer is used as the resin component (a), it is preferably used as a mixture of the acrylic monomer and its polymer. This mixture has a desired viscosity in which (ii) an acrylic polymer is dissolved in a monomer liquid containing (i) an acrylic monomer as a main component and, if necessary, other vinyl monomer for copolymerization. It is particularly preferable that it is a mixture (syrup) in the state. As a method for obtaining this syrup, for example, a method of polymerizing an acrylic monomer to stop the progress of the polymerization at a certain point, or, for example, using an acrylic monomer obtained by suspension polymerization as a main constituent unit There is a method of dissolving a beaded polymer in an acrylic monomer. As an advantage of using a mixture such as syrup, for example, 1) when aluminum hydroxide is added to the resin component, the precipitation of aluminum hydroxide can be prevented by controlling the viscosity, and 2) the curing time of the resin component is shortened. Can be mentioned.

The unsaturated polyester used as the resin component (a) comprises an unsaturated polybasic acid or an acid anhydride thereof (if necessary, a saturated polybasic acid or an acid anhydride thereof is also used) and a polyhydric alcohol. Obtained by polycondensation. In particular, α,
An unsaturated polyester obtained by polycondensation of β-unsaturated dibasic acid or its acid anhydride, aromatic saturated dibasic acid or its acid anhydride, and glycols is desirable. In some cases, an unsaturated polyester obtained by using an aliphatic or alicyclic saturated dibasic acid or an acid anhydride thereof in combination is also desirable. In addition, unsaturated polyester modified with vinyl at the terminal, and vinyl ester modified with vinyl modified at the terminal of epoxy skeleton can also be used. When an unsaturated polyester is used, it is usually an unsaturated monomer (α, β-unsaturated monomer, etc.) for crosslinking the unsaturated polyester.
Then, the unsaturated polyester is dissolved and used as a so-called unsaturated polyester resin. This ratio is 30 to 80 parts by weight of unsaturated polyester and 70 to 2 of unsaturated monomer.
0 parts by weight is desirable.

Α for the synthesis of unsaturated polyesters,
Examples of β-unsaturated dibasic acids or acid anhydrides thereof include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid and esters thereof, and glycols include ethylene glycol. , Propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,
4-butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, Examples thereof include ethylene glycol carbonate. As the aromatic saturated dibasic acid or its acid anhydride which is used in combination as necessary, phthalic acid,
Examples thereof include phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, diphenic acid, tetrahydrophthalic anhydride and halogenated phthalic anhydride. Aliphatic or alicyclic saturated dibasic acid or its acid to be used in combination as necessary. Examples of the anhydride include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, and their esters. Examples of the unsaturated monomer for crosslinking the unsaturated polyester include styrene, vinyltoluene, α-methylstyrene, chlorostyrene, dichlorostyrene, vinylnaphthalene, ethyl vinyl ether, methyl vinyl ketone, methyl (meth) acrylate and ethyl. Examples thereof include vinyl compounds such as (meth) acrylate and allyl compounds such as diallyl phthalate, diallyl fumarate and diallyl succinate.

In order to cure the resin component (a) as described above, a curing catalyst is usually used together. Examples of the curing catalyst include tertiary butyl peroxymaleic acid, benzoyl peroxide, cumene hydroperoxide, tertiary butyl hydroperoxide, dicumyl peroxide, acetyl peroxide, lauroyl peroxide, and azobisisobutyronitrile. . In the case of polymerizing and curing at room temperature, for example, peroxides and amines, peroxides and sulfinic acids, combinations of peroxides and cobalt compounds, peroxy compounds such as tertiary butyl peroxymaleic acid and glycol dimercaptoacetate. And the like, and combinations thereof with water (deionized water, etc.). When an unsaturated polyester resin is used, examples of the curing catalyst include methyl ethyl ketone peroxide and the like, and examples of the curing accelerator include cobalt naphthenate and the like.

Aluminum hydroxide (b) used in the present invention
Is an inorganic filler that gives the artificial marble a desired appearance, hardness, elastic modulus, and the like. Further, in the present invention, the aluminum hydroxide (b) in the composition (M1) is a component that further enhances the effectiveness of the antibacterial agent (c) containing zinc oxide and imparts anti-MRSA properties. Composition (M
In 1) and (M2), aluminum hydroxide (b) is
10 to 90 parts by weight is used for 100 parts by weight of the resin component and aluminum hydroxide in total. The lower limit of the amount used is more preferably 20 parts by weight or more, preferably 45 parts by weight or more, and more preferably 50 parts by weight or more. The upper limit is preferably 88 parts by weight or less. Regarding the particle size of aluminum hydroxide (b), considering the influence of the increase in viscosity when mixed with the resin component (a), the average particle size is 10 to 10.
100 μm is preferable. In addition, methacrylsilane (γ-
Those surface-treated with a silane coupling agent such as methacryloxypropyltrimethoxysilane) are preferable.

Inorganic fillers other than aluminum hydroxide,
It can be used in combination within a range that does not impair the effects of the present invention. As the inorganic filler used in combination, calcium hydroxide, magnesium hydroxide, powder talc, powder quartz, fine silica, diatomaceous earth, gypsum, powder glass, clay minerals, powder chalk,
Marble, limestone, aluminum silicate, calcium silicate, borax, calcium sulfite, calcium sulfate, barium sulfate, silicon dioxide, calcite, base stone, titanium oxide,
Antimony trioxide, clay, aluminum oxide, calcium carbonate, nickel powder, iron powder, zinc powder, copper powder, iron oxide,
Examples thereof include glass beads, glass fibers, glass fillers containing barium salt or lead salt, silica gel, zirconium oxide, tin oxide and the like.

The antibacterial agent (c) used in the present invention is an anti-MRS.
It is a component to be used in combination with the aluminum hydroxide (b) in the composition (M1) and dispersed in the artificial marble for the purpose of giving A property. The antibacterial agent (c) is not particularly limited as long as it contains zinc oxide as an active ingredient, and various conventionally known antibacterial agents can be used. Specifically, zinc oxide powder, a mixture of zirconium phosphate and silver oxide / zinc oxide (for example, Toa Gosei Co., trade name Novalon), a mixture of zeolite and silver oxide / zinc oxide (for example, product of Sinanen Co., Ltd. Zeomix), a mixture of calcium phosphate and zinc oxide (for example, Sangi Co., trade name Apacider), and the like can be used. When the zinc oxide powder is used alone, its average particle size is preferably 0.2 μm to 100 μm, more preferably 0.2 μm to 50 μm, and more preferably 0.2.
2 μm to 10 μm is particularly preferable. The amount of the antibacterial agent (c) used in the composition (M1) is 0.1 to 10.0 parts by weight based on 100 parts by weight of the total of the resin component and aluminum hydroxide. Further, regarding the lower limit of this usage amount, 0.
The amount is preferably 3 parts by weight or more, and more preferably 0.5 parts by weight or more. The upper limit is preferably 8.0 parts by weight or less.

In the present invention, in addition to the above components, various components conventionally known as additive components for artificial marble can be used without limitation. For example, white (titanium oxide, zinc sulfide), yellow (iron oxide yellow), black (iron oxide black), red (iron oxide red), blue (ultramarine blue, phthaloblue) pigments, dyes, etc.
Examples thereof include an ultraviolet absorber, a flame retardant, a release agent, a fluidizing agent, a thickener, a polymerization inhibitor and an antioxidant.

Among the above components, at least 90 to 10 parts by weight of the resin component (a) and aluminum hydroxide (b) 1
A composition (M1) comprising 0 to 90 parts by weight, and 0.1 to 10.0 parts by weight of an antibacterial agent (c) containing zinc oxide, based on 100 parts by weight of the resin component and aluminum hydroxide in total. By polymerizing and curing, mainly anti-M
A thin layer that contributes to the RSA property can be formed. In addition, a composition (M2) containing at least 90 to 10 parts by weight of the resin component (a) and 10 to 90 parts by weight of aluminum hydroxide (b) among the above-mentioned respective components [A point not containing the antibacterial agent (c)] Is different from (M1)], the resin layer constituting the main part of the artificial marble can be formed, and the anti-MRSA artificial marble having the two-layer structure of the present invention can be obtained. The components [excluding the antibacterial agent (c)] and the composition ratios in the compositions (M1) and (M2) are preferably the same, but different components and composition ratios may be used as desired. Moreover, the layer thickness of each layer may be appropriately determined as desired, but the thickness of the thin layer formed from the composition (M1) is preferably about 1 to 10 mm, and more preferably 1 to 3 mm.
The degree is more preferable. The thickness of the resin layer formed from the composition (M2) may be appropriately determined according to the desired size of the artificial marble and the like, but is preferably about 4 to 10 mm. Since the artificial marble of the present invention has a two-layer structure in which the antibacterial agent is added only to the thin layer portion in this manner, while maintaining the original physical properties of the artificial marble (mechanical properties, thermal properties, durability, etc.), It also has the effect of reducing manufacturing costs compared to the case where an antibacterial agent is added to the entire artificial marble.

As a method of polymerizing the compositions (M1) and (M2), there are a redox polymerization method and a method of heating polymerization after adding a thermal initiator. For example, redox polymerization of a polymer having an acrylic monomer as a main constituent unit is carried out by acyl peroxide such as benzoyl peroxide and N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethylpara. It is carried out by a combination with an amine compound such as toluidine or a combination of a peroxyl compound such as tertiary butyl peroxymaleic acid and a mercaptan compound such as glycol dimercaptoacetate.

The compositions (M1) and (M2) are cured in a mold to give an anti-M having a two-layer structure having a desired shape.
An RSA artificial marble is obtained. As the molding method, any of casting molding, injection molding, compression molding and the like can be applied, but casting molding is preferable.

In the production method of the present invention, after forming a thinner layer than the composition (M1) in the mold, the composition (M1) is formed.
2) or a resin layer is formed from the composition (M2) and then a thin layer is formed from the composition (M1) in the mold. Of these manufacturing methods, when the resin layer is formed after the thin layer is formed, the thin layer is appropriately cured instead of forming the second layer (resin layer) while the thin layer is still fluid. Optimally, the second layer is formed once it has begun or after it has fully cured. On the other hand, when the thin layer is formed after the resin layer is formed, the second layer (thin layer) may be formed without waiting for the curing of the first layer (resin layer).

The surface of the molded product after curing is preferably ground with sandpaper, a sponge-like abrasive (trade name: Scotchbright), or the like. In addition, for the purpose of making the surface of the artificial marble a desired stone pattern or sand pattern, the artificial marble of the same material is crushed into a crushed shape in advance,
This is mixed with the composition (M1) or (M2), molded,
It is also possible to obtain an artificial marble exhibiting such a pattern.
In this case, the crushed material (crunch) does not necessarily need to contain the antibacterial agent (c). Even if the antibacterial agent (c) -free crushed material (crunch) is added to the composition (M1) in an amount of 10 to 20% by weight, the same good anti-MRSA property can be obtained.

[0025]

EXAMPLES Examples of the present invention will be described below. In the following description, “part” and “%” are based on weight unless otherwise specified.

<Example 1 and Comparative Example 1> Poly (methyl methacrylate) and methyl methacrylate (weight ratio 2:
A syrup consisting of 8) was prepared. 25 of this syrup
The viscosity at ° C was 50 centipoise. Example 1
In this case, the total amount of this syrup and aluminum hydroxide powder having an average particle diameter of 45 μm (manufactured by Nippon Light Metal Co., Ltd.) is 100.
Parts (ratio of aluminum hydroxide is shown in Table 1), tertiary butyl peroxymaleic acid (Nippon Yushi Co., trade name Perbutyl MA) 0.3 parts, ethylene glycol dimethacrylate (Mitsubishi Rayon Co., trade name Acryester) ED) 0.35 part, ethylene glycol dimercaptoacetate 0.15 part, deionized water 0.1 part, white pigment (titanium oxide) 0.9 part, average particle size 0.5 as an antibacterial agent
Predetermined amount of zinc oxide (made by Sakai Chemical Industry) of 5 μm (listed in Table 1)
Mix and degas under vacuum with stirring. By injecting this vacuum degassed mixture into a mold and curing at room temperature,
A thin layer having a thickness of 0.5 to 1.3 mm was molded in a mold. Then, a composition having the same composition except that the antibacterial agent was not included was molded in the mold to form a resin layer, thereby obtaining a sheet-like cured product having a two-layer structure and a thickness of 13 mm. This surface was ground with # 120 sandpaper to obtain an acrylic artificial marble having a two-layer structure. This surface roughness was 1.7 μm.

In Comparative Example 1, as shown in Table 1,
An acrylic artificial marble having a two-layer structure was obtained in the same manner as in Example 1 except that either zinc oxide or aluminum hydroxide powder as an antibacterial agent was not added to the thin layer.

The acrylic artificial marble having a two-layer structure obtained in Example 1 and Comparative Example 1 described above was tested for anti-MRSA and anti-coli properties. The test method is as shown below. 1) Test bacterium Staphylococcus aureus IID 1677 (MRSA) Escherichia coli IFO 3301 (E. coli) IID 1677 was obtained from the Institute of Medical Science, University of Tokyo by IFO 3
301 is publicly available from the Fermentation Research Institute. 2) Preparation of bacterial solution Using ordinary broth medium (Eiken Chemical Co., Ltd.) at 35 ° C., 16-2
The culture broth of the test bacterium, which had been shake-cultured for 0 hours, was diluted 10,000 times with a sterile phosphate buffer solution to give a bacterium solution. 3) Test operation 0.5 ml of the bacterial solution was dropped on the test surface of the sample and stored in a closed system at 25 ° C., and the viable cell count of the sample was measured at 6 hours and 24 hours after storage. The same test was performed using 0.5 ml of the bacterial solution dropped on a sterile plastic petri dish as a control sample. 4) SCDLP medium (manufactured by Nippon Pharmaceutical Co., Ltd.) was used as a viable cell count sample and control sample.
The cells were washed out with 10 ml each, and the number of viable cells was measured by the pour plate culture method (cultured at 35 ° C. for 48 hours) using a standard agar medium for this washout, and converted into a sample and a control sample.

The results are shown in Tables 1 and 2 below.

[0030]

[Table 1]

[0031]

[Table 2] As shown in Table 1, in Example 1 in which zinc oxide and aluminum hydroxide powder as antibacterial agents are used together, excellent anti-MR is obtained.
Comparative Example 1 in which SA property is expressed but only one is added
Then, sufficient anti-MRSA properties cannot be obtained. Moreover, the results shown in Table 2 show that even if zinc oxide and aluminum hydroxide are used in combination, no particularly excellent effect is exhibited in terms of anti-E. Coli. That is, it has no anti-coli properties but anti-MRSA
It shows the peculiarity of the present invention that there is a property.

<Example 2 and Comparative Example 2> As the antibacterial agent, a mixture of zirconium phosphate, silver oxide and zinc oxide (manufactured by Toa Gosei Co., Ltd., trade name NOVALON AGZ-330, hereinafter abbreviated as "NOVALON") is used. Example 1 except what was done
Then, an acrylic artificial marble was prepared in the same manner as in Comparative Example 1 and tested for anti-MRSA property (6 hours after storage). The results are shown in Table 3 below.

[0033]

[Table 3] As shown in Table 3, in Example 2 in which Novalon as an antibacterial agent and aluminum hydroxide powder are used in combination, excellent anti-MR is obtained.
Comparative Example 2 in which SA property is expressed but only one is added
Then, sufficient anti-MRSA properties cannot be obtained.

<Example 3> Zinc oxide (a) having different particle size or purity, manufactured by Sakai Chemical Co., Ltd., average particle size 0.26 to 0.28μ
m, purity 99.5%, (b) average particle size 0.5 to 0.6 μ
m, purity 99.5%, (c) average particle size 0.5 to 0.6 μ
m, purity 99.0%, Example 1
Acrylic artificial marble is prepared in the same manner as in
Tested for sex. The results are shown in Table 4 below.

[0035]

[Table 4] As shown in Table 4, even when the particle size of zinc oxide is changed, the same excellent anti-MRSA property is exhibited.

Example 4 An acrylic artificial marble was prepared in the same manner as in Example 1 except that deionized water (hardening cocatalyst) was not used, and tested for anti-MRSA property.
The results are shown in Table 5 below.

[0037]

[Table 5] As shown in Table 5, when an antibacterial agent containing zinc oxide and aluminum hydroxide are used in combination, excellent anti-MRSA properties are exhibited regardless of the presence or absence of deionized water (curing promoter).

<Example 5> Artificial marble prepared in advance (the same as Example 1 except that the antibacterial agent (c) is not included).
Crushed to 7-10 mesh crushed material (crunch)
Got Add this crunch to the mixture for 10-20
An acrylic artificial marble was produced in the same manner as in Example 2 except that the addition of the weight% (described in Table 6) was performed, and the anti-MRSA property was tested. The results are shown in Table 6 below.

[0039]

[Table 6] As shown in Table 6, 1 crunch containing no antibacterial agent (c) was used.
The same good anti-MRSA property can be obtained even when 0 to 20% by weight is added.

Comparative Example 3 An acrylic artificial marble was prepared in the same manner as in Example 1 except that zinc sulfide was used instead of zinc oxide, and tested for anti-MRSA and anti-coli properties. The results are shown in Table 7 below.

[0041]

[Table 7] As shown in Table 7, it is understood that when zinc sulfide is used, the excellent effects of the present invention cannot be obtained at all.

<Example 6 and Comparative Example 4> An unsaturated polyester resin (manufactured by Showa High Polymer Co., Ltd.) Rigolac), aluminum hydroxide powder having an average particle size of 45 μm (manufactured by Nippon Light Metal Co., Ltd.), 100 parts in total (aluminum hydroxide ratio is shown in Table 8), curing catalyst (55% methyl ethyl ketone peroxide) 1 part, curing acceleration 0.15 parts of agent (6% cobalt naphthenate), 0.9 parts of white pigment (titanium oxide), and a predetermined amount of zinc oxide (Sakai Chemical Co., Ltd.) having an average particle diameter of 0.55 μm as an antibacterial agent (described in Table 8). Mix and degas under vacuum with stirring. The vacuum degassed mixture was poured into a mold to form a thin layer having a thickness of 0.5 to 1.3 mm in the mold. After that, a composition having the same composition except that an antibacterial agent was not included was molded in the mold to form a resin layer, thereby obtaining a sheet-like cured product having a two-layer structure and a thickness of 13 mm. This surface was ground with # 120 sandpaper to obtain an unsaturated polyester artificial marble having a two-layer structure. This surface roughness was 1.7 μm. Also in this example, as in Example 1, as a curing catalyst, tertiary butyl peroxymaleic acid 0.35 part, ethylene glycol dimethacrylate 0.35 part, ethylene glycol dimercaptoacetate 0.15 part, deionized Water 0.1
Parts may be used.

In Comparative Example 4, as shown in Table 8,
An unsaturated polyester artificial marble having a two-layer structure was obtained in the same manner as in Example 6, except that either zinc oxide or aluminum hydroxide powder as an antibacterial agent was not added to the thin layer.

With respect to the unsaturated polyester artificial marble having a two-layer structure obtained in Example 6 and Comparative Example 4 above, anti-MR
Tested for SA and E. coli. The results are shown in Tables 8 and 9 below.

[0045]

[Table 8]

[0046]

[Table 9] As shown in Tables 8 and 9, also in the unsaturated polyester artificial marble, as in the case of the acrylic artificial marble (Tables 1 and 2), the special and excellent effect regarding the anti-MRSA property of the present invention is exhibited.

<Example 7 and Comparative Example 5> An unsaturated polyester artificial marble was prepared in the same manner as in Example 6 except that Novalon was used as the antibacterial agent, and tested for anti-MRSA property (6 hours after storage. Progress). The results are shown in Table 10 below.

[0048]

[Table 10] As shown in Table 10, also in the unsaturated polyester artificial marble, the effect regarding the anti-MRSA property of the present invention is exhibited similarly to the acrylic artificial marble (Table 3).

<Example 8> Zinc oxide (a) having a different particle size or purity, manufactured by Sakai Chemical Co., Ltd., average particle size 0.26 to 0.28 μm.
m, purity 99.5%, (b) average particle size 0.5 to 0.6 μ
m, purity 99.5%, (c) average particle size 0.5 to 0.6 μ
m, purity 99.0%, Example 6
Prepare an unsaturated polyester artificial marble in the same manner as
Tested for anti-MRSA properties. The results are shown in Table 11 below.
Shown in.

[0050]

[Table 11] As shown in Table 11, even in the unsaturated polyester artificial marble, the effect regarding the anti-MRSA property of the present invention is exhibited similarly to the acrylic artificial marble (Table 4).

Example 9 An unsaturated polyester artificial marble was prepared in the same manner as in Example 6 except that deionized water (hardening cocatalyst) was not used, and tested for anti-MRSA property. The results are shown in Table 12 below.

[0052]

[Table 12] As shown in Table 12, also in the unsaturated polyester artificial marble, the effect regarding the anti-MRSA property of the present invention is exhibited similarly to the acrylic artificial marble (Table 5).

<Example 10> An artificial marble prepared in advance (the same as in Example 6 except that the antibacterial agent (c) was not included) was crushed to obtain a 7-10 mesh crushed material (crunch). It was Add 10% of this crunch to the total amount of the mixture.
An unsaturated polyester artificial marble was produced in the same manner as in Example 7 except that 20% by weight (described in Table 13) was added, and the anti-MRSA property was tested. The results are shown in Table 13 below.

[0054]

[Table 13] As shown in Table 13, also in the unsaturated polyester artificial marble, the effect regarding the anti-MRSA property of the present invention is exhibited similarly to the acrylic artificial marble (Table 6).

<Comparative Example 6> An unsaturated polyester artificial marble was prepared in the same manner as in Example 6 except that zinc sulfide was used instead of zinc oxide, and tested for anti-MRSA property and anti-Escherichia coli property. The results are shown in Table 14 below.

[0056]

[Table 14] As shown in Table 14, it is understood that when zinc sulfide is used, the excellent effects of the present invention cannot be obtained at all.

[0057]

As described above, the artificial marble of the present invention is an artificial marble having an anti-MRSA property which cannot be obtained by the prior art. Further, since the artificial marble of the present invention has a two-layer structure in which an antibacterial agent is added only to the thin layer portion, the artificial marble is maintained while maintaining various physical properties (mechanical properties, thermal properties, durability, etc.) inherent to the artificial marble. It also has the effect of reducing manufacturing costs compared to the case where an antibacterial agent is added to the entire marble.

Further, the production method of the present invention is a method which can be carried out easily and satisfactorily, and can reduce the production cost as compared with the production method in which an antibacterial agent is added to the entire artificial marble.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C08K 3/20 C08K 3/20 C08L 101/00 C08L 101/00 // B29K 33:04 B29K 33:04 67:00 67:00 105: 16 105: 16 (56) Reference JP-A-8-26805 (JP, A) JP-A-7-266522 (JP, A) JP-A-8-27306 (JP, A) JP-A-9-71727 (JP, A) JP-A-7-242456 (JP, A) Actual development Sho 60-32027 (JP, U) (58) Fields investigated (Int.Cl. ⁷ , DB name) B32B 1/00-35 / 00 B29C 39/00-39/44 C04B 26/00-26/32

Claims (4)

(57) [Claims] 1. An antibacterial agent containing zinc oxide based on 90 to 10 parts by weight of a resin component (a), 10 to 90 parts by weight of aluminum hydroxide (b), and 100 parts by weight of the resin component and aluminum hydroxide in total. (C) 0.1 to 10.0
A thin layer formed from a composition (M1) containing 1 part by weight, 90 to 10 parts by weight of a resin component (a) and 10 to 90 parts by weight of aluminum hydroxide (b), and an antibacterial agent (c). An anti-MRSA artificial marble having a two-layer structure with a resin layer formed from a non-composition (M2). 2. The resin component (a) is composed of at least one selected from the group consisting of melamine (meth) acrylate, glycidyl (meth) acrylate, methyl (meth) acrylate and unsaturated polyester. Anti-MRSA artificial marble. 3. A resin component (a) 90-1 in a mold
0 parts by weight, 10 to 90 parts by weight of aluminum hydroxide (b), and an antibacterial agent (c) containing zinc oxide with respect to 100 parts by weight of the resin component and aluminum hydroxide in total.
After forming a thin layer from the composition (M1) containing 0.1 to 10.0 parts by weight, 90 to 10 parts by weight of the resin component (a) and 10 to 90 parts by weight of aluminum hydroxide (b) are included. A method for producing an anti-MRSA artificial marble having a two-layer structure, including a step of forming a resin layer from a composition (M2) containing no antibacterial agent (c). 4. A resin component (a) 90-1 in a mold
After forming a resin layer from a composition (M2) containing 0 parts by weight and 10 to 90 parts by weight of aluminum hydroxide (b) and not containing an antibacterial agent (c) containing zinc oxide, a resin component (a) 90 to 10 parts by weight, 10 to 90 parts by weight of aluminum hydroxide (b), and 0.1 to 10.0 parts by weight of antibacterial agent (c) containing zinc oxide based on 100 parts by weight of the resin component and aluminum hydroxide in total. A method for producing an anti-MRSA artificial marble having a two-layer structure, comprising the step of forming a thin layer from the composition (M1) containing