JP2001233646A - Artificial marble holding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a clean and hygienic artificial marble molding by improving stain resistance and controlling proliferation of mold and bacterium in an artificial marble molding. SOLUTION: The stain resistance on the surface of artificial marble molding can be improved by an fine uneven structure 7 on the surface and a synergistic effect of a silane coupling agent 1 and an additive 2 by making the artificial marble molding which has the fine uneven structure 7 on the surface and is composed of a resin component 6, an inorganic filler 5, the silane coupling agent 1 and the additive 2 having a surface free energy smaller than that of the resin component 6.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an artificial marble molded article having excellent stain resistance.

[0002]

2. Description of the Related Art Artificial marble formed to have a natural marble appearance by incorporating various inorganic fillers and pigments into a resin component such as an unsaturated polyester resin is used for bathtubs, washing places, countertops, and kitchens. It is often used for top boards, sanitary applications, furniture, interior materials, etc. These artificial marbles are generally composed of resins, inorganic fillers, low shrinkage agents, catalysts, cross-linking agents, pigments, etc., and are formed by casting, hot pressing, etc., and are relatively inexpensive and workable and workable. It has excellent warm water resistance, strength, and weather resistance, has an appearance close to that of natural marble, and has a luxurious feeling.

[0003]

In recent years, along with the diversification of lifestyles, the consciousness of cleanliness has spread among young people, especially among young people. However, artificial marble moldings used especially in places around water such as kitchens, washrooms, and bathrooms are apt to become dirty, and bacteria and mold grow on the dirt as bait, and the appearance and hygiene are improved. There was a problem. Therefore, an object of the present invention is to realize an artificial marble molded article in which the aforementioned artificial marble molded article is easily stained and the problem that bacteria and mold are easily proliferated is eliminated.

[0004]

In order to solve the above-mentioned problems, the present invention has fine irregularities on the surface, and a resin component, an inorganic filler, a silane coupling agent, and a resin having a surface free energy of the resin component. And an additive of a substance smaller than the surface free energy.

When the surface of the artificial marble has a fine uneven structure, the following Wenzel's equation holds.

Γ cos θ = cos θ ′ (1) where γ: true artificial marble surface area / apparent artificial marble surface area θ: true liquid (water) contact angle θ ′: apparent liquid (water) contact angle Since γ> 1 in the equation (1), if θ> 90 °, θ <θ ′. Therefore, if the surface free energy of the artificial marble is sufficiently small, a synergistic effect with the fine uneven structure of the artificial marble surface is extremely large. An artificial marble having water repellency can be obtained, and interaction with a dirt component is reduced, so that antifouling property is greatly improved. In addition, bacteria and mold also have less adhesion of their prey, and thus their growth is also suppressed.

Further, the silane coupling agent covers the surface of the inorganic filler, and further reacts with the resin component and improves compatibility. Therefore, the inorganic filler and the resin caused by the curing shrinkage of the resin component during molding of the artificial marble molded article, etc. Reduces the gap created between components. This makes it difficult for the dirt component to penetrate and adhere to the gap, thereby greatly improving antifouling properties. In addition, the surface energy of the artificial marble compact decreases due to the effect of additives with small surface free energy,
The water repellency is greatly improved by a synergistic effect with the fine uneven structure on the surface, and the interaction with the dirt component is reduced, so that the antifouling property is extremely improved. Further, by reacting the additive with the resin component, the resin component, the additive, the silane coupling agent, and the inorganic filler are integrated, and the artificial marble molded body itself having a fine uneven structure on the surface has a water repellency. And the antifouling durability is greatly improved. Bacteria and mold also have a small amount of adhered dirt components serving as their baits, so that their growth is also suppressed.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention provides a bathtub, a washing place, a countertop, a kitchen top plate,
It can be applied to sanitary applications, various furniture, interior materials, and the like.

That is, according to the first aspect of the present invention, the surface free energy of the resin component, the inorganic filler, the silane coupling agent, and the surface free energy of the resin component is smaller than that of the resin component. This is an artificial marble molded product containing an additive of a small substance.

Since the surface of the artificial marble contains a fine uneven structure and an additive having a small surface free energy, the surface of the artificial marble is significantly improved in water repellency, and has a low activity against a dirt component. Components are less likely to adhere. In addition, the silane coupling agent reacts and coats the surface of the inorganic filler, and further reacts with the resin component and improves compatibility. Reduce the gap that can be created. This makes it difficult for the dirt component to penetrate and adhere to the gap, and the amount of dirt component adhering is greatly reduced. The anti-fouling property of the surface of the artificial marble molding is greatly improved by the fine uneven structure of the surface of the artificial marble and the synergy effect of the additive and the silane coupling agent. As a result, bacteria and mold also have a small amount of adhered dirt components serving as their baits, so that their growth is suppressed.

Further, according to the present invention, the roughness of the fine uneven structure on the surface does not exceed 500 μm, and the resin component, the inorganic filler, the silane coupling agent, and the surface free energy of the resin component are reduced. An artificial marble molded article containing an additive of a substance smaller than the surface free energy.

The fine unevenness has a roughness of 500 μm.
By not exceeding m, the true surface area of the artificial marble molded product increases, the synergistic effect with the low surface free energy additive material increases, the water repellency of the artificial marble molded product surface is extremely improved, and The affinity for the components is greatly reduced. Furthermore, since the adhesion of the dirt component to the surface of the artificial marble molded article is greatly reduced, the growth of mold and bacteria that feed on them is greatly suppressed.

Further, the invention according to claim 3 is an artificial marble molded product comprising at least one silane coupling agent selected from the group reacting with a resin component and an inorganic filler.

The silane coupling agent reacts and coats the surface of the silane coupling agent by binding with the inorganic filler, and further reacts with the resin component. As a result, the inorganic filler and the resin component are firmly bonded via the silane coupling agent to be integrated. As a result, at the time of curing and molding of the artificial marble molded product, the gap formed between the inorganic filler and the resin component generated by the curing shrinkage of the resin component is reduced, and the ingress and attachment of the dirt component is suppressed.

[0015] The invention according to claim 4 is an artificial marble molded article using an organic silicon compound as an additive.

With the very low surface free energy effect of the organosilicon compound, the water repellency of the surface of the artificial marble molded article can be greatly improved with a smaller amount of addition.
Combined with the silane coupling agent and the synergistic effect with the fine uneven structure on the surface of the artificial marble molded product, the antifouling property of the surface of the artificial marble molded product is improved.

Further, the invention according to claim 5 is an artificial marble molded product comprising at least one organic silicon compound selected from the group having reactivity with a resin component.

The water repellency of the artificial marble is greatly improved by reacting the organic silicon compound with the resin component and integrating the same. In other words, the antifouling durability is greatly improved by a synergy effect with the fine uneven structure of the surface of the artificial marble molded product.

Further, the invention according to claim 6 provides an artificial resin comprising a resin component comprising at least one selected from the group consisting of melamine (meth) acrylate, glycidyl (meth) acrylate, methyl (meth) acrylate and unsaturated polyester. It is a marble molding.

[0020] The resin component is composed of at least one selected from the group consisting of melamine (meth) acrylate, glycidyl (meth) acrylate, methyl (meth) acrylate and unsaturated polyester. It has excellent physical and chemical properties such as strength, durability and hot water resistance. The inorganic filler and the resin component are firmly bonded and integrated by the silane coupling agent, and a gap formed between the inorganic filler and the resin component generated by the curing shrinkage of the resin component during the curing molding of the artificial marble molding. And the infiltration and adhesion of the dirt component is suppressed. And with the very low surface free energy effect of the organosilicon compound, it becomes possible to greatly improve the water repellency of the artificial marble surface with a smaller amount of addition,
Combined with the silane coupling agent and the synergistic effect with the fine concavo-convex structure of the surface of the artificial marble, the antifouling property of the surface of the artificial marble is improved. Further, the organic silicon compound reacts with and integrates with the resin component, whereby the water-repellent durability, that is, the antifouling durability of the artificial marble molded product is greatly improved.

Further, the invention according to claim 7 is an artificial marble molded product in which the resin component is a mixture of an acrylic monomer and a polymer thereof.

Further, since the resin component is composed of a mixture of an acrylic monomer and a polymer thereof,
The artificial marble molded article has excellent texture, and further, has excellent physical properties and chemical properties such as mechanical properties, weather resistance, and hot water resistance. The inorganic filler and the resin component are firmly bonded and integrated by the silane coupling agent, and a gap formed between the inorganic filler and the resin component generated by the curing shrinkage of the resin component during the curing molding of the artificial marble molding. And the infiltration and adhesion of the dirt component is suppressed. And, with the extremely low surface free energy effect of the organosilicon compound, the water repellency of the artificial marble surface can be significantly improved with a smaller amount of addition, and the silane coupling agent and fine irregularities on the surface of the artificial marble molded product can be improved. Combined with the synergistic effect with the structure, the antifouling property of the surface of the artificial marble molding is improved. Further, the organic silicon compound reacts with and integrates with the resin component, whereby the water-repellent durability, that is, the antifouling durability of the artificial marble molded product is greatly improved.

The invention according to claim 8 is an artificial marble molded article having a fine uneven structure on the surface and containing a resin component, an inorganic filler, a silane coupling agent, an organic silicon compound, and an antibacterial agent. It is what it was.

Then, the silane coupling agent reacts and coats the surface of the silane coupling agent by binding with the inorganic filler, and further reacts with the resin component. As a result, the inorganic filler and the resin component are firmly bonded via the silane coupling agent to be integrated. Thereby, at the time of hardening molding of the artificial marble molded body, a gap formed between the inorganic filler and the resin component generated by the curing shrinkage of the resin component is reduced, and the penetration and adhesion of the dirt component are suppressed. In addition, the extremely low surface free energy effect of the organosilicon compound makes it possible to significantly improve the water repellency of the artificial marble surface with a small amount of addition, and the silane coupling agent and the fine irregularities on the artificial marble molded product surface Combined with the synergistic effect with the structure, the antifouling property of the surface of the artificial marble molding is improved. In addition, when the organic silicon compound has reactivity with the resin component, the organic silicon compound reacts with the resin component to be integrated, thereby significantly improving the water repellency durability, that is, the antifouling durability of the artificial marble molded product. Is done.

According to a ninth aspect of the present invention, there is provided an artificial marble comprising a resin component, an inorganic filler, a silane coupling agent, an organosilicon compound, at least one inorganic antibacterial agent, and at least one organic antibacterial agent. It was a molded article.

[0026] By containing an inorganic antibacterial agent, the growth of bacteria mainly causing slimming is suppressed. In addition, by containing an organic antibacterial agent, mold growth is mainly suppressed. The addition of a silane coupling agent, an organosilicon compound, and a fine uneven structure on the surface of the artificial marble molded product reduces the attachment of dirt components that serve as bait for bacteria and mold. A small amount of antibacterial agent has a sufficient effect. For this reason, the influence on the physical properties and chemical properties of the artificial marble molded article is small, and an artificial marble molded article having excellent properties can be obtained.

The roughness of the fine concavo-convex structure of the present invention may not be uniform. Further, the shape of the concavo-convex structure is not particularly limited, and may be any one of a spherical surface, a scale, a prism, a column, a pyramid, a cone, a needle, and the like. Further, the shape may be a complicated combination of those shapes. There is no particular limitation on the method of forming such a concavo-convex structure, and it may be an artificially processed one or a naturally existing one. In particular, as a method of artificially processing, 1. A method of sanding the surface of the artificial marble molded product with a paper file or a metal file. Sandblasting,
3. 3. A method of cutting a V-groove or a cross hatch with a cutter. There is, but not particularly limited to, a method of forming an artificial marble by molding an artificial marble on a surface of a mold having fine irregularities on the surface to obtain a fine irregular structure of the mold on the surface. . Further, the roughness of the fine uneven structure is preferably 500 μm or less, and if it exceeds 500 μm, the effect is reduced. Further, when the roughness becomes extremely fine and approaches a flat surface, the effect is reduced.

The resin component in the present invention is not particularly limited as long as it is a resin that can be cured to form artificial marble. Various types of monomers and monomers and polymers that have been conventionally known as resin components for artificial marble are used. And the like can be used as appropriate. For example, unsaturated polyester, melamine (meth) acrylate, glycidyl (meth) acrylate, methyl (meth) acrylate and the like can be mentioned.
In this specification, (meth) acryl means acryl and / or methacryl. Specific examples of the (meth) acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth).
Examples include, but are not limited to, acrylates and benzyl (meth) acrylates.

As inorganic fillers, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, powdered talc, powdered quartz, fine silica, diatomaceous earth, gypsum, powdered glass, clay mineral, powdered chalk, marble, limestone, silicic acid Aluminum, calcium silicate, borax, calcium sulfite, calcium sulfate, barium sulfate, silicon dioxide, calcite, titanium oxide, antimony trioxide, clay,
Examples include, but are not limited to, aluminum oxide, calcium carbonate, nickel powder, iron powder, zinc powder, copper powder, iron oxide, glass beads, glass fiber, glass filler having a barium salt or lead salt, silica gel, and the like. is not.

Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ
-Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacrylic Roxypropyltriethoxysilane, N-β (aminoethyl)
γ-aminopropylmethyldimethoxysilane, N-β
(Aminoethyl) γ-aminopropyl metrimethoxysilane and the like, but are not limited thereto.

The additives that can be used in the present invention are not particularly limited as long as they have a surface free energy smaller than that of the resin component. Organic silicon compounds are suitable as additives, and these may be used alone or in a mixture.

As the organic silicon compound, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, non-reactive silicone compounds whose side chains or terminals are polyether-modified, and whose terminals are alkyl-modified , Higher fatty acid ester-modified, higher alkoxy-modified, etc., but are not limited thereto. Reactive silicone compounds such as methylhydrogenpolysiloxane, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc., amino-modified, epoxy-modified, carboxy-modified, or carboxy-modified Examples thereof include those modified with knol and those modified with methacryl, but are not limited thereto.

The antibacterial agent in the present invention includes silver nitrate, silver sulfate, silver chloride and the like as inorganic antibacterial agents. Silver, copper, zinc, or tin-supported zeolites, and silver, copper,
Examples thereof include silica gel supporting zinc or tin, but are not limited thereto.

Examples of the organic antibacterial agent include phenyl ether derivatives such as 10,10'-oxybisphenoxaarsine, N-haloalkylthio compounds such as cyclofluanide, and 2- (4-thiazolyl) benzimidazole (hereinafter abbreviated as TBZ). Imidazole derivatives, 2, 3, etc.
Examples include, but are not limited to, quaternary ammonium salts such as 5,6 tetrachloro-4- (methylsulfolyl) pyridine.

[0035]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, specific embodiments of the present invention will be described in detail.

Example 1 100 parts by weight of an unsaturated polyester resin comprising a mixture of an isophthalic unsaturated polyester and styrene, 200 parts by weight of aluminum hydroxide powder, and 3 parts by weight of 50% benzoyl peroxide as a curing catalyst 0.03 parts by weight of dimethylaniline as a curing accelerator, 0 and 5 parts by weight of γ-methacryloxypropylmethyldimethoxysilane as a silane coupling agent, and 4 parts by weight of methacryl-modified organopolysiloxane are sufficiently stirred and mixed with a kneader. did. Insert the mixture into the mold and cure,
An artificial marble compact was obtained. Furthermore, a fine uneven structure was formed on the surface of the artificial marble molding by sandblasting.

(Example 2) 100 parts by weight of an unsaturated polyester resin comprising a mixture of an isophthalic acid-based unsaturated polyester and styrene, 200 parts by weight of aluminum hydroxide powder, and 3 parts by weight of 50% benzoyl peroxide as a curing catalyst. 0.03 parts by weight of dimethylaniline as a curing accelerator, 0 and 5 parts by weight of γ-methacryloxypropylmethyldimethoxysilane as a silane coupling agent, and 4 parts by weight of an alkyl-modified organopolysiloxane are sufficiently stirred and mixed in a kneader. did. The mixture was inserted into a mold and cured to obtain an artificial marble molded product. Furthermore, a fine uneven structure was formed on the surface of the artificial marble molding by sandblasting.

(Example 3) 100 parts by weight of an unsaturated polyester resin comprising a mixture of an isophthalic unsaturated polyester and styrene, 200 parts by weight of aluminum hydroxide powder, and 3 parts by weight of 50% benzoyl peroxide as a curing catalyst. 0.03 parts by weight of dimethylaniline as a curing accelerator, 0 and 5 parts by weight of γ-methacryloxypropylmethyldimethoxysilane as a silane coupling agent, 4 parts by weight of methacryl-modified organopolysiloxane, and 1 part by weight of silver zeolite. 0.5 parts by weight of TBZ was sufficiently stirred and mixed with a kneader. The mixture was inserted into a mold and cured to obtain an artificial marble molded product. Furthermore, a fine uneven structure was formed on the surface of the artificial marble molding by sandblasting.

Example 4 100 parts by weight of an unsaturated polyester resin consisting of a mixture of an isophthalic unsaturated polyester and styrene, 200 parts by weight of aluminum hydroxide powder, and 3 parts by weight of 50% benzoyl peroxide as a curing catalyst 0.03 parts by weight of dimethylaniline as a curing accelerator, 0 and 5 parts by weight of γ-methacryloxypropylmethyldimethoxysilane as a silane coupling agent, 4 parts by weight of methacryl-modified organopolysiloxane, and 4 parts by weight of silver zeolite. 2 parts by weight of TBZ was sufficiently stirred and mixed with a kneader. The mixture was inserted into a mold and cured to obtain an artificial marble molded product. Furthermore, a fine uneven structure was formed on the surface of the artificial marble molding by sandblasting.

FIG. 1 is a schematic view showing a surface portion of an artificial marble molded body in this embodiment. 1 is a silane coupling agent represented by γ-methacryloxypropylmethyldimethoxysilane. 2 is an additive represented by a methacryl-modified organopolysiloxane. 3 is an inorganic antibacterial agent represented by silver zeolite. 4 is an organic antibacterial agent represented by TBZ. 5 is an inorganic filler represented by aluminum hydroxide. 6 is a resin component represented by an unsaturated polyester resin. The silane coupling agent 1 is coated on the surface of the inorganic filler 5 by reaction coating, and further reacts with the resin component 6 to form an integral unit. 7 is a fine uneven structure on the surface of the artificial marble molded product. In addition, 8 shows a water drop and 9 shows a dirt component.

FIG. 2 is a schematic view showing a surface portion of an artificial marble molded product in a conventional example.

Example 5 100 parts by weight of a syrup composed of polymethyl methacrylate and methyl methacrylate at a weight ratio of 2: 8, and aluminum hydroxide powder 2
00 parts by weight, tert-butyl peroxymaleic acid 0.5 part by weight, ethylene glycol dimethacrylate 0.5 part by weight, ethylene glycol dimethyl captoacetate 0.3 part by weight, and γ-methacrylic acid as a silane coupling agent. 0 and 5 parts by weight of roxypropylmethyldimethoxysilane and 4 parts by weight of a methacryl-modified organopolysiloxane were sufficiently stirred and mixed with a kneader. The mixture was inserted into a mold and cured to obtain an artificial marble molded product. Furthermore, a fine uneven structure was formed on the surface of the artificial marble molding by sandblasting.

Example 6 100 parts by weight of syrup composed of polymethyl methacrylate and methyl methacrylate at a weight ratio of 2: 8, and aluminum hydroxide powder 2
00 parts by weight, tert-butyl peroxymaleic acid 0.5 part by weight, ethylene glycol dimethacrylate 0.5 part by weight, ethylene glycol dimethyl captoacetate 0.3 part by weight, and γ-methacrylic acid as a silane coupling agent. 0 and 5 parts by weight of roxypropylmethyldimethoxysilane, 4 parts by weight of a methacryl-modified organopolysiloxane, 4 parts by weight of silver zeolite and 2 parts by weight of TBZ were sufficiently mixed with a kneader by stirring. The mixture was inserted into a mold and cured to obtain an artificial marble molded product. Furthermore, a fine uneven structure was formed on the surface of the artificial marble molding by sandblasting.

Comparative Example 1 100 parts by weight of an unsaturated polyester resin consisting of a mixture of an isophthalic unsaturated polyester and styrene, 200 parts by weight of aluminum hydroxide powder, and 3 parts by weight of 50% benzoyl peroxide as a curing catalyst. Then, 0.03 parts by weight of dimethylaniline as a curing accelerator and 4 parts by weight of methacryl-modified organopolysiloxane were sufficiently stirred and mixed with a kneader. The mixture was inserted into a mold and cured to obtain an artificial marble molded product.

Comparative Example 2 100 parts by weight of an unsaturated polyester resin comprising a mixture of an isophthalic unsaturated polyester and styrene, 200 parts by weight of aluminum hydroxide powder, and 3 parts by weight of 50% benzoyl peroxide as a curing catalyst. Then, 0.03 parts by weight of dimethylaniline as a curing accelerator was sufficiently stirred and mixed in a kneader. The mixture was inserted into a mold and cured to obtain an artificial marble molded product.

Comparative Example 3 100 parts by weight of an unsaturated polyester resin composed of a mixture of an isophthalic unsaturated polyester and styrene, 200 parts by weight of aluminum hydroxide powder, and 3 parts by weight of 50% benzoyl peroxide as a curing catalyst. Then, 0.03 parts by weight of dimethylaniline as a curing accelerator, 1 part by weight of silver zeolite, and 0.5 part by weight of TBZ were sufficiently stirred and mixed with a kneader. The mixture was inserted into a mold and cured to obtain an artificial marble molded product.

The water repellency of the surface of each molded product obtained in each of the examples and comparative examples was measured with a contact angle measuring device (model CA-Z) manufactured by Kyowa Interface Chemical Co., Ltd. In addition, contamination resistance is determined by JI
It was confirmed according to SK3370. The stain resistance was compared visually, and the degree of contamination in Comparative Example 1 was evaluated as Δ, worse was evaluated as x, and better was evaluated as relative. The results are shown in (Table 1).

[0048]

[Table 1]

Next, each molded article obtained in Example 1 and Example 2 was subjected to a 50 ° C. hot water immersion test for 40 hours, and a test was conducted for water repellency. The results are shown in (Table 2).

[0050]

[Table 2]

Next, tests were carried out on the antibacterial performance and the mold resistance of each molded article obtained in each of the examples and comparative examples. A 50 mm × 50 mm sample was cut out from the molded body, and 1 cc of Staphylococcus aureus and Escherichia coli were each added.
Was added dropwise and cultured at 37 ° C. for 24 hours. Thereafter, the bacteria were washed out with a sterilized phosphate buffer. The viable cell count in the washed-out liquid was measured by a pour plate method using a cell count medium. The results are shown in (Table 3).

[0052]

[Table 3]

Each Aspergillus niger solution was sprayed on each sample of 50 mm × 50 mm placed on an agar medium, and the mixture was sprayed at 25 ° C. for 7 minutes.
Cultured for days. The results are shown in (Table 4).

[0054]

[Table 4]

Next, the slimming resistance of each molded product obtained in each of the examples and comparative examples was evaluated.

To the bath water after bathing, 0.02% of ordinary broth, which is a nutrient of the bacterium, was added to obtain a slimy culture solution. 40 ℃
The sample cut from the molded body was suspended in the culture solution kept at a constant temperature for 5 days, and the slime was adhered. The sample surface was actually touched, and a slimy sensory test was performed. Based on the degree of sliminess, the grading was applied to the four-level evaluation. When almost no sliminess was felt, ◎ was given, when a little slimming was felt, 場合 when considerable slimming was felt, △, and when strong slimming was felt, × was marked. evaluated. The results are shown in (Table 5).

[0057]

[Table 5]

As is clear from Table 1, Example 1,
The molded articles 2, 3, 4, 5, and 6 had improved stain resistance compared to Comparative Example 1. At the same time, the water repellency was significantly improved as compared with Comparative Examples 2 and 3, and the stain resistance was also greatly improved. From these results, it can be seen that the water repellency and stain resistance of the artificial marble are significantly improved by a synergy effect of the silane coupling agent, the organosilicon compound additive, and the fine uneven structure on the surface of the artificial marble. It was revealed. Further, even if the resin component is an unsaturated polyester resin or an acrylic resin, the effect remains unchanged, and a clean and clean artificial marble molded product can be realized.

As is clear from Table 2, the molded article of Example 1 was able to obtain better water-repellent durability than that of Example 2. From these results, it is possible to realize an artificial marble molded product having good water repellency and durability by using an organic silicon compound additive that can react with a resin component.

As is clear from Table 3, Example 3,
The molded articles of Nos. 4 and 6 were Comparative Examples 1 and 2 and Example 1,
A remarkable antibacterial effect on Staphylococcus aureus and Escherichia coli could be obtained as compared with the molded articles 2 and 5. The artificial marble molded product to which the organosilicon compound is added is difficult to adhere to the surface as a bait for bacteria due to a synergy effect with the fine uneven structure of the surface of the artificial marble molded product. It is possible to obtain a clean and clean artificial marble compact in which the growth of bacteria is suppressed with a smaller amount of an antibacterial agent.

As is clear from (Table 4), Example 3
The molded articles of Nos. 4 and 6 were Comparative Examples 1 and 2 and Example 1,
Good antifungal performance was obtained as compared with the molded products of Nos. 2 and 5. Artificial marble compacts with the addition of organosilicon compounds are:
Synthetic effect with the fine uneven structure of the surface of the artificial marble molded product makes it difficult for the surface to become dirty with bacteria and fungi, so when used in combination with an organic antibacterial agent, the growth of mold can be achieved with a smaller amount of antibacterial agent. Thus, it is possible to obtain a clean and clean artificial marble molded article in which the generation of the marble is suppressed.

As is clear from Table 5, the artificial marble is good due to the synergistic effect with the silane coupling agent, the organic silicon compound additive, the inorganic antibacterial agent and the fine uneven structure on the surface of the artificial marble. Develops excellent slimming resistance. Due to the synergistic effect between the silane coupling agent, the organic silicon compound additive, and the fine uneven structure of the surface of the artificial marble, the amount of dirt components adhering to the surface of the artificial marble is small, and the proliferation of bacteria causing slimming is small. In addition, since the dead body of bacteria which directly causes the slimming does not easily adhere, the slimming resistance is improved. Furthermore, the addition of a small amount of an antibacterial agent can extremely effectively suppress the occurrence of slime.

[0063]

According to the artificial marble molding of the present invention as described above, the following effects can be obtained.

The invention according to claim 1 is an additive of a substance having a fine uneven structure on the surface, a resin component, an inorganic filler, a silane coupling agent, and a material having a surface free energy smaller than the surface free energy of the resin component. And an artificial marble molded article containing:

By containing the fine irregular structure of the surface of the artificial marble and the additive having a small surface free energy,
The surface of the artificial marble molded article has significantly improved water repellency and low activity against dirt components, so that dirt components are less likely to adhere. In addition, the silane coupling agent reacts and coats the surface of the inorganic filler, and further reacts with the resin component and improves compatibility. Reduce the gap that can be created. This makes it difficult for the dirt component to penetrate and adhere to the gap, and the amount of dirt component adhering is greatly reduced. The anti-fouling property of the surface of the artificial marble molding is greatly improved by the fine uneven structure of the surface of the artificial marble and the synergy effect of the additive and the silane coupling agent. As a result, bacteria and mold also have a small amount of adhered dirt components serving as their baits, so that their growth is suppressed.

Further, according to the present invention, the roughness of the fine uneven structure on the surface does not exceed 500 μm, and the resin component, the inorganic filler, the silane coupling agent, and the surface free energy of the resin component are reduced. An artificial marble molded article containing an additive of a substance smaller than the surface free energy. By preventing the roughness of the fine uneven structure from exceeding 500 μm, the true surface area of the artificial marble molding increases, the synergy with the low surface free energy additive increases, and the surface of the artificial marble molding increases. The water repellency is greatly improved, and the affinity for the dirt component is greatly reduced. Furthermore, since the adhesion of the dirt component to the surface of the artificial marble molded article is greatly reduced, the growth of mold and bacteria that feed on them is greatly suppressed.

Further, the invention according to claim 3 is an artificial marble molded article comprising at least one silane coupling agent selected from the group reacting with a resin component and an inorganic filler. The silane coupling agent reacts and coats the surface by binding with the inorganic filler, and further reacts with the resin component. As a result, the inorganic filler and the resin component are firmly bonded via the silane coupling agent to be integrated. Thereby, at the time of hardening and molding of the artificial marble molded body, the gap formed between the inorganic filler and the resin component generated by the curing shrinkage of the resin component is reduced, and the penetration and adhesion of the spill component is suppressed.

The invention according to claim 4 provides an artificial marble molded product using an organic silicon compound as an additive. With the extremely low surface free energy effect of the organosilicon compound, it is possible to significantly improve the water repellency of the surface of the artificial marble with a small amount of addition, and the silane coupling agent and fine irregularities on the surface of the artificial marble Combined with the synergistic effect with the structure, the antifouling property of the surface of the artificial marble molding is improved.

Further, the invention according to claim 5 is an artificial marble molded product comprising at least one organic silicon compound selected from the group having reactivity with a resin component.
The water repellency durability of the artificial marble molded article is greatly improved by reacting and integrating the organic silicon compound with the resin component.
In other words, the antifouling durability is greatly improved by a synergy effect with the fine uneven structure of the surface of the artificial marble molded product.

Further, the invention according to claim 6 is an artificial resin comprising a resin component composed of at least one selected from the group consisting of melamine (meth) acrylate, glycidyl (meth) acrylate, methyl (meth) acrylate and unsaturated polyester. It is a marble molding. By forming the resin component from at least one selected from the group consisting of melamine (meth) acrylate, glycidyl (meth) acrylate, methyl (meth) acrylate and unsaturated polyester, the artificial marble molded product has mechanical strength, durability, It has excellent physical and chemical properties such as hot water resistance. The inorganic filler and the resin component are firmly bonded and integrated by the silane coupling agent, and a gap formed between the inorganic filler and the resin component generated by the curing shrinkage of the resin component during the curing molding of the artificial marble molding. And the infiltration and adhesion of the dirt component is suppressed. And, with the extremely low surface free energy effect of the organosilicon compound, the water repellency of the artificial marble surface can be significantly improved with a smaller amount of addition, and the silane coupling agent and fine irregularities on the surface of the artificial marble molded product can be improved. Combined with the synergistic effect with the structure, the antifouling property of the surface of the artificial marble molding is improved. Further, the organic silicon compound reacts with and integrates with the resin component, whereby the water-repellent durability, that is, the antifouling durability of the artificial marble molded product is greatly improved.

The invention according to claim 7 is an artificial marble molded product in which the resin component is a mixture of an acrylic monomer and a polymer thereof. By the resin component is composed of a mixture of acrylic monomer and its polymer,
The artificial marble molded article has excellent texture, and further, has excellent physical properties and chemical properties such as mechanical properties, weather resistance, and hot water resistance. The inorganic filler and the resin component are firmly bonded and integrated by the silane coupling agent, and a gap formed between the inorganic filler and the resin component generated by the curing shrinkage of the resin component during the curing molding of the artificial marble molding. And the infiltration and adhesion of the dirt component is suppressed. And, with the extremely low surface free energy effect of the organosilicon compound, the water repellency of the artificial marble surface can be significantly improved with a smaller amount of addition, and the silane coupling agent and fine irregularities on the surface of the artificial marble molded product can be improved. Combined with the synergistic effect with the structure, the antifouling property of the surface of the artificial marble molding is improved. Further, the organic silicon compound reacts with and integrates with the resin component, whereby the water-repellent durability, that is, the antifouling durability of the artificial marble molded product is greatly improved.

The invention according to claim 8 provides an artificial marble molded article having a fine uneven structure on the surface and containing a resin component, an inorganic filler, a silane coupling agent, an organic silicon compound, and an antibacterial agent. It is what it was.

The silane coupling agent reacts and coats the surface of the silane coupling agent by binding to the inorganic filler, and further reacts with the resin component. As a result, the inorganic filler and the resin component are firmly bonded via the silane coupling agent to be integrated. Thereby, at the time of hardening molding of the artificial marble molded body, a gap formed between the inorganic filler and the resin component generated by the curing shrinkage of the resin component is reduced, and the penetration and adhesion of the dirt component are suppressed. In addition, the extremely low surface free energy effect of the organosilicon compound makes it possible to significantly improve the water repellency of the artificial marble surface with a small amount of addition, and the silane coupling agent and the fine irregularities on the artificial marble molded product surface Combined with the synergistic effect with the structure, the antifouling property of the surface of the artificial marble molding is improved. In addition, when the organic silicon compound has reactivity with the resin component, the organic silicon compound reacts with the resin component to be integrated, thereby significantly improving the water repellency durability, that is, the antifouling durability of the artificial marble molded product. Is done.

The invention according to claim 9 is an artificial marble comprising a resin component, an inorganic filler, a silane coupling agent, an organosilicon compound, at least one inorganic antibacterial agent, and at least one organic antibacterial agent. It was a molded article.

[0075] By containing an inorganic antibacterial agent, the growth of bacteria mainly causing slime is suppressed. In addition, by containing an organic antibacterial agent, mold growth is mainly suppressed. The addition of a silane coupling agent, an organosilicon compound, and a fine uneven structure on the surface of the artificial marble molded product reduces the attachment of dirt components that serve as bait for bacteria and mold. A small amount of antibacterial agent has a sufficient effect. For this reason, the influence on the physical properties and chemical properties of the artificial marble molded article is small, and an artificial marble molded article having excellent properties can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic view showing a surface portion of an artificial marble molded body according to a fourth embodiment of the present invention.

FIG. 2 is a schematic view showing a surface portion of a conventional artificial marble molding.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Silane coupling agent 2 Additive 3 Inorganic antibacterial agent 4 Organic antibacterial agent 5 Inorganic filler 6 Resin component 7 Fine uneven structure

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/544 C08K 5/544 C08L 83/04 C08L 83/04 101/00 101/00 // C08J 7 / 00 C08J 7/00 Z (C04B 26/02 (C04B 26/02 Z 24:42) 24:42) Z 103: 69 103: 69 (72) Inventor Naoko Ikukawa 1006 Kazuma, Oji, Kadoma, Osaka Prefecture Matsushita Electric Within Sangyo Co., Ltd. (72) Inventor Masaaki Yonemura 1006 Kadoma, Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.F-term (reference) BB01 BC03 BC08 4F073 AA06 BA18 BA23 BB01 GA05 GA11 4J002 BG071 CF211 CP032 DA076 DA078 DA086 DA106 DA108 DD078 DE076 DE126 DE136 DE146 DE236 DF038 DG046 DG048 DG056 DJ006 DJ016 DJ036 DJ046 DK006 DM00 6 ED058 EV298 EV348 EX037 EX067 EX077 FD016 FD147 FD188 FD202

Claims (9)

[Claims] 1. A resin having a fine uneven structure on its surface, a resin component, an inorganic filler, a silane coupling agent, and an additive of a substance having a surface free energy smaller than the surface free energy of the resin component. An artificial marble molded body made of 2. The artificial marble according to claim 1, wherein the roughness of the fine uneven structure does not exceed 500 μm. 3. The artificial marble according to claim 1, wherein the silane coupling agent is at least one selected from the group having reactivity with the resin component and the inorganic filler. 4. The method according to claim 1, wherein the additive comprises an organosilicon compound.
4. The artificial marble molded product according to any one of items 3 to 3. 5. The artificial marble molding according to claim 4, wherein the organosilicon compound is at least one selected from the group having reactivity with the resin component. 6. The resin component comprises melamine (meth) acrylate, glycidyl (meth) acrylate, methyl (meth)
The artificial marble molding according to any one of claims 1 to 5, comprising at least one selected from the group consisting of acrylates and unsaturated polyesters. 7. The resin component according to claim 1, wherein the resin component comprises a mixture of an acrylic monomer and a polymer thereof.
The molded article of artificial marble described in the above item. 8. An artificial marble molded article having a fine uneven structure on the surface and comprising a resin component, an inorganic filler, a silane coupling agent, an organosilicon compound, and an antibacterial agent. 9. The artificial marble according to claim 8, wherein the antibacterial agent comprises at least one of an inorganic antibacterial agent and at least one of an organic antibacterial agent.