JPH11157899A - Antifungal artificial marble and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an artificial marble product low in price and capable of obtaining a high antifungal effect even if the amount of an antifungal agent is small by a molding method such as a pressure molding by heating at high temperature, BMC and SMC which are impossible heretofore and to produce the antifungal artificial marble product hardly causing discoloring, excellent in light resistance and good in physical property and appearance even when a silver-based antifungal agent is used by using the antifungal agent good in dispersibility. SOLUTION: In this antifungal artificial marble molded by the pressure molding by heating, the antifungal agent or the antifungal agent and an inorg. auxiliary material are dispersed in the whole product, and these are abundantly aggregated near surface layer side. The antifungal agent is a silver-based antifungal agent carrying at least one kind among silver compd., silver ion, silver complex salt or silver complex ion on an inorg. carrier, and an ion exchange type or soluble carrier is used as the inorg. carrier and the inorg. auxiliary material. After subjecting the antifungal agent or the silver based antifungal agent to mixing agitation in a resin material, the resin paste in which a packing material, etc., are mixed by agitation is arranged in a mold and pressurized.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a system kitchen,
The present invention relates to an artificial marble product such as a top plate used for a vanity table and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Generally, artificial marble products used around water in kitchens, washrooms, etc. are liable to generate mold and bacteria depending on conditions such as temperature and humidity. In addition, in public facilities used by unspecified people, the tendency is stronger due to the addition of conditions such as pollution. As a means to solve this problem, an anti-fungal agent, an antibacterial agent and the like for preventing mold and bacteria are mixed and dispersed in a resin material to produce an artificial marble product. There is an antibacterial artificial marble product having an antibacterial effect by forming a surface layer with a mixture of an antibacterial agent and the like.

[0003] In addition, as a method for producing these antibacterial artificial marble products, a method in which a mold-inhibiting agent and an antibacterial agent are kneaded in a resin is filled into a molding die, or the product is formed on the inner molding surface of the molding die. After applying a gel coat resin in which a fungicide / antimicrobial agent is dispersed, a molding material is injected and molded, and a surface antimicrobial layer is formed by a casting method of transferring the antimicrobial gel coat layer to the molding material surface, or The antibacterial agent / antibacterial agent is formed on the surface of a preformed article by applying a coating material in which a fungicide / antibacterial agent is dispersed to form a surface antibacterial layer.

[0004] An antibacterial artificial marble product is produced by such a manufacturing method, and a bulk molding compound (BM) is prepared by using a resin material in which an antibacterial agent is mixed and dispersed.
C), heat and pressure molding of a sheet molding compound (SMC), etc., is generally performed by adding a filler and an additive to a resin material at the same time or after adding an antibacterial agent to the resin material. Since the antimicrobial agent is added and mixed and stirred, the dispersibility of the antimicrobial agent is poor, and there is a case where the antimicrobial agent does not exist in the surface layer having the most antimicrobial effect. Therefore, the antibacterial effect does not work even on the surface layer unless the amount of the antibacterial agent used for the resin material is increased, so that a large amount of the antibacterial agent is required, which significantly increases the cost and cannot be realized. Was.

When a silver-based antibacterial agent is used,
Artificial marble products mixed with silver-based antibacterial agents cause discoloration due to silver eluting into the resin or becoming unstable when excited by ultraviolet rays and reacting with the curing accelerator, causing discoloration. Since the light resistance was deteriorated in portions other than the containing portion, it was not possible to obtain a product having good physical properties and appearance permanently.

[0006]

DISCLOSURE OF THE INVENTION The present invention relates to a heat and pressure molding method for molding by applying high heat, a bulk molding compound (BMC), and a sheet molding compound which could not be conventionally used by using an antibacterial agent having good dispersibility. It is an object of the present invention to make it possible to produce an artificial marble product which is inexpensive and can provide a high antibacterial effect even in a small amount even by a molding method such as (SMC). It is another object of the present invention to obtain an antibacterial artificial marble product which is free from discoloration, has excellent light resistance, and has good physical properties and appearance even when a silver-based antibacterial agent is used.

[0007]

According to the present invention, an antibacterial agent or an antibacterial agent and an inorganic auxiliary material are dispersed throughout an artificial marble product formed by heat and pressure molding. Antimicrobial artificial marble composed of a resin material layer in which an antimicrobial agent and an inorganic auxiliary material are largely dispersed near the surface layer side.

The antibacterial agent is a silver-based antibacterial agent having at least one of a silver compound, silver ion, silver complex salt or silver complex ion supported on the surface of an inorganic carrier, and comprises an inorganic carrier and an inorganic auxiliary material. Uses an ion exchange type or dissolution type carrier. The addition amount of these antibacterial agents or silver-based antibacterial agents is 0.1 to 5.0% by weight of the whole main material. The mixing ratio with the auxiliary material is 9: 1 to 6: 4. In addition, after mixing and stirring an antibacterial agent or a silver-based antibacterial agent in a resin material, a resin paste added with a filler or the like and mixed and stirred is divided and disposed in a lower mold, and an upper mold is formed. After setting, heat and pressure are applied to produce antibacterial artificial marble. In order to reinforce the product, after adding fillers and mixing and stirring,
A reinforcing material may be added to the resin paste.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION As the molding material used in the present invention, various synthetic resins which can be subjected to heat molding using a molding die can be used, and polyester resins, acrylic resins and unsaturated polyester resins can be used. And a resin material such as vinyl ester resin and epoxy resin.
Pigments may be appropriately added and mixed. Further, for the purpose of reinforcing and preventing deformation of the artificial marble product, for example, aluminum hydroxide, silica, glass frit, calcium carbonate and the like can be used as a filler. In order to further increase the strength, a glass fiber sheet, glass fiber chip, carbon fiber, organic fiber, or the like can be used as a reinforcing material.

The antibacterial agent used in the present invention includes silver ion,
Antibacterial using silver complex salts such as silver complex salts, silver complex ions, or silver compounds such as silver nitrate, silver sulfate, silver lactate, silver chlorate, silver fluoride, silver pixonate, silver phosphate and silver phosphite alone Agent A, or zeolite, zirconium phosphate,
The silver-based antibacterial agent B in which the antibacterial agent A used alone is supported on various inorganic supports such as aluminum phosphate, lithium-based crystallized glass, and water-soluble glass can be used. As the inorganic auxiliary material, an ion-exchange type carrier such as zeolite and zirconium phosphate, or a dissolution type carrier such as aluminum phosphate, lithium crystallized glass, and water-soluble glass can be used. The additives are a low shrinkage agent, a pigment, a thixotropic agent, a peroxide polymerization initiator and the like.

[0011]

Embodiments of the present invention will be described below. These examples illustrate one embodiment of the present invention and do not limit the present invention. Next, a method of manufacturing the antibacterial artificial marble product 20 will be described along the manufacturing process of the present invention.

FIG. 1 shows a molding apparatus and a manufacturing process for producing a compressed resin sheet 14 of the present invention.
1 shows a molding apparatus and a manufacturing process for obtaining an antibacterial artificial marble product 20 using the compressed resin sheet 14. FIG. 3 shows the antibacterial effect. FIG. 4 is a diagram showing a discoloration effect. The molding apparatus 1 shown in FIG. 1 is an apparatus for forming a compressed resin sheet 14, and a first polyethylene film supply device 8, a belt conveyor 2, and a winding device 10 are disposed below the molding device 1. A first resin having a stirring device for stirring the resin material and the additives therein above the polyethylene film supply device 8, and having supply pipes 3a and 3b for supplying a bifurcated resin paste C at a lower portion; A hopper 3 and a reinforcing material supply hopper 4 provided with a cutter 5 for cutting the reinforcing material supplied from a device (not shown) for supplying the reinforcing material into a chop shape are provided.

Below the reinforcing material supply hopper 4, the supply pipes 3a and 3b for supplying the resin paste C extended from the first resin hopper 3, and below the supply pipes 3a and 3b, the resin paste C is provided. In order to reduce the emission area,
A pair of impregnating rolls 6a installed at a predetermined interval,
6b is provided. The supply pipes 3a and 3b are filled with the resin paste C supplied by the supply pipes 3a and 3b along the outer circumference of the impregnation rolls 6a and 6b.
Are disposed so as to be discharged and dropped together with the inward rotation of the impregnating rolls 6a and 6b from the gaps of. Below the impregnating rolls 6a and 6b, a scraping roll 7 is provided. On the other hand, a first polyethylene film 8a wound in a roll shape, a roll fixing device 8b rotatably fixing the first polyethylene film 8a, and a transport roller 8c
And a first polyethylene film supply device 8 composed of an inclined plate 8d and disposed below the scraping roll 7.
Continuing with the first polyethylene film supply device 8,
The belt conveyor 2 is provided continuously, and the belt conveyor 2
The winding device 10 is arranged near the end of the winding device.

The first polyethylene film is slid from a roll fixing device 8b via a conveying roller 8b on an inclined plate arranged at a sharp inclination below the scraping roll 7, and is connected to a belt conveyor connected thereto. 2, and is wound by the winding device 10 while moving along with the rotation of the belt conveyor 2. Further, it is composed of a second polyethylene film 9a wound in a roll shape, a roll fixing device 9b rotatably fixing the second polyethylene film 9a, a first transport roller 9c, and a second transport roller 9d. Second polyethylene film supply device 9
Is disposed below the scraping roll 7 and above the belt conveyor 2. The second polyethylene film supply device 9 is connected to the belt conveyor 2 which is arranged continuously with the first polyethylene film supply device 8.

The second conveyor roller 9d is a belt conveyor 2
A predetermined distance from the surface of the belt conveyor 2 and a predetermined distance from the tip of the inclined plate are provided above the start end of the belt conveyor 2. The second polyethylene film is supplied from the roll fixing device 9b to the first transport roller 9c.
Then, via the second conveyor roller 9d, it moves on the connected belt conveyor 2 and is wound by the winding device 10.

Further, a pressing device 11 is disposed above the belt conveyor 2 at a position parallel to the second transport roller 9d with an interval toward the end of the belt conveyor 2. Thereby, the resin paste C mixed with the chop-shaped reinforcing material
Is scraped off onto the first polyethylene film and falls, and then, together with the first polyethylene film, is transferred to the belt conveyor 2.
The resin paste C that moves upward and is mixed with a chop-like reinforcing material with the second polyethylene film 9a supplied from above
And the resin paste C is pressed from above the second polyethylene film 9 a by the pressing device 11 to form the compressed resin sheet 14.

The molding apparatus 2 shown in FIG. 2 is an apparatus for molding an antibacterial artificial marble product 20 using the compressed resin sheet 14, and includes a molding die including an upper die 21 and a lower die 22, and a molding die (not shown). It consists of a pressure device and a heating device. In the present embodiment, each of the above-mentioned molding devices is adopted, but the present invention is not limited to the above-mentioned device specifications.

Next, up to the completion of the antibacterial artificial marble will be described along the manufacturing process. (Step: 1) In a first resin hopper 3 into which 29% by weight of an unsaturated polyester resin is put in 100% by weight of the whole main material, a silver-based antibacterial agent B containing a silver compound supported on zirconium phosphate ( Toa Gosei: AG300) Particle size 1.3 to
1.5 μm is 0.2 to 100% by weight of the whole main material.
4% by weight, and a particle diameter of 1.3 to 1.5 as an inorganic auxiliary material
μm zirconium phosphate 100% by weight
0.06% by weight with respect to the mixture. The main material is, in this embodiment, an unsaturated polyester resin,
Shows calcium carbonate, curing accelerators, low shrinkage agents, and pigments.

(Step: 2) Thereafter, 60% by weight of calcium carbonate having a particle size of 8 to 300 μm is used as a filler in this unsaturated polyester resin and 4% by weight of a curing accelerator, a low shrinkage agent, a pigment and the like as an additive. % And further mixed and stirred to prepare a resin paste C containing a silver-based antibacterial agent B. Although zirconium phosphate was mixed in (step: 1), it may be mixed in (step: 2).

(Step: 3) Plate glass fibers 12 for reinforcing the artificial marble product 20 are supplied from above the reinforcing material supply hopper 4, and cut into the reinforcing material supplying hopper 4 while being cut into a chop shape by the cutter 5. The filled and chopped glass fibers 13 fall from the lower opening of the reinforcing material supply hopper 4. The resin paste C supplied from the supply pipes 3a and 3b sandwiches the chop-like reinforcing material from both sides along the outer circumference of the impregnation roll 6, and also impregnates the chop-like glass fiber 13 with the resin paste C and with the chop-like glass fiber. The glass fiber is dropped, scraped down by the scraping roll 7, and dropped onto the first polyethylene film while the chopped glass fiber and the resin paste C are mixed. The chopped glass fiber is 7% by weight of the total material weight of 100% by weight. In this embodiment, a glass fiber chip is used as a reinforcing material. However, any material can be used as long as the reinforcing material is an inorganic powder such as glass powder.

(Step: 4) Mixed resin paste C
Falls on the first polyethylene film 8a,
Along with the first polyethylene film 8a, the slant slides on the inclined plate 8d along the inclined plate, and is eluted on the continuously-moving rotating belt conveyor 2.

(Step: 5) The resin paste C that has reached the belt conveyor 2 is brought into contact with the second polyethylene film passed to the second transport roller 9d, and is adjusted to a constant thickness by the second transport roller 9d. Then, while covering the second polyethylene film, the resin paste C is applied to the first polyethylene film 8a and the second polyethylene film.
Is conveyed in the direction of the terminal end of the belt conveyor 2 together with the belt by the rotation of the belt conveyor 2 in a sandwiched state. Thereafter, the resin paste C is applied to the pressing device 11.
Is pressed from above the second polyethylene film 9a, and the compressed resin sheet 14 is formed.

(Step: 6) This compressed resin sheet 14
Is wound by the winding device 10 in a sandwich state while moving on the belt conveyor 2, and the compressed resin sheet 14 is completed.

(Step: 7) The upper mold 21 is previously heated to 150 ° C.
Then, the lower mold 22 is heated to 140 ° C., the compressed resin sheet 14 is cut into a predetermined size, the polyethylene film is removed, and several laminated sheets are charged into the lower mold 22. Is set, pressurized while evacuating with vacuum, and then cured and molded.

(Step: 8) After molding, the product is cooled and demolded to obtain an artificial marble product 20. The obtained artificial marble product 20 was obtained in which the silver-based antibacterial agent B and zirconium phosphate were dispersed throughout the product, and a large amount of the silver-based antibacterial agent B was aggregated near the surface layer.

[0026]

[Operation] As shown in this example, a resin paste C is used in which a silver-based antibacterial agent B and zirconium phosphate are uniformly mixed in advance in an unsaturated polyester resin, and a filler is added and mixed. When the compressed resin sheet 14 containing the antibacterial agent is prepared and disposed in the heated lower mold 22, the compressed resin sheet 14 begins to slightly decrease in viscosity from the molding surface 22 a of the lower mold 22, and the upper mold 21 is set. , Molding surface 21 of upper mold 21
The viscosity is also reduced from a. When the viscosity of the compressed resin sheet 14 in the mold is reduced, the filler and the additive having a large particle size are removed from the lower mold 2.
The silver-based antibacterial agent B and zirconium phosphate, which gradually begin to harden while dropping to the molding surface of No. 2 and have a small particle size and are uniformly impregnated with the unsaturated polyester resin on the peripheral surface, are unsaturated polyester resin. Of the upper die 21 having a reduced viscosity, flows near the molding surface 21a, rises, and gradually begins to harden. In addition, since the inorganic auxiliary material has a small particle size, the silver-based antimicrobial agent B is formed near the molding surface 21a of the upper mold 21 together with the flow of the unsaturated polyester resin having reduced viscosity.
And begins to cure around the middle layer, fillers and additives.

Since the upper mold 21 is heated at a temperature higher by 10 ° C. than the lower mold 22, the viscosity near the molding surface 21 a of the upper mold 21 becomes lower due to the temperature difference between the upper mold 21 and the lower mold 22. However, once the viscosity of the compressed resin sheet 14 has been reduced, it hardens quickly from the upper mold 21 heated at a high temperature, so that the silver-based antibacterial material near the molding surface 21a of the upper mold 21 having reduced viscosity is obtained. Agent B and zirconium phosphate are used on molding surface 2 of upper mold 21.
1a, the silver-based antibacterial agent B and the zirconium phosphate near the molding surface 22a of the lower mold 22 are removed.
Before reaching 1a, it cures around the intermediate layer, fillers and additives to cure.

For this reason, compared to using a resin composition in which a filler and an additive are added to a resin material at the same time or after that and an antibacterial agent is added and mixed and stirred, as compared with the conventional resin material, Even with the use of an antimicrobial agent, the antimicrobial agent appears on the surface of the artificial marble product 20.

[0029]

[Effect] As shown in FIG. 3, an artificial marble product was placed in a sealed container, Escherichia coli was placed on the product, and the effect was confirmed over the elapsed time (1, 6, and 24 hours). As a result of confirming the antibacterial effect, a comparison between a sample containing no antibacterial agent (blank), a sample containing a silver-carrying antibacterial agent and an inorganic auxiliary material (sample 1), and a sample containing only a silver-carrying antibacterial agent (sample 2) was obtained.
In the (blank), E. coli proliferated, and in (Sample 1) and (Sample 2), E. coli died and could not be detected.

As shown in FIG. 4, as a result of confirming the color difference effect, as compared with (blank), since (Sample 1) and (Sample 2) contain silver, the color difference value increases, and discoloration is confirmed. However, when comparing (Sample 1) and (Sample 2) containing the same silver, the color difference value and the discoloration were much smaller in the sample (Sample 1) containing the inorganic auxiliary material.

In the present invention, since the antibacterial agent is added to the resin material in advance, mixed and agitated, and then the filler is added. Therefore, even when heating and pressure molding of a bulk molding compound, a sheet molding compound, or the like is performed. In addition, the antibacterial agent is dispersed throughout the artificial marble product, and an artificial marble product having a large amount of the antibacterial agent collected near the product surface can be obtained, and a high antibacterial effect can be obtained. or,
Because high antibacterial effect can be obtained even with a small amount of antibacterial agent,
Significant cost reduction can be achieved. Also, by adding reinforcement,
Products can also be strengthened.

Further, when a silver-based antibacterial agent is used in a resin, silver is eluted and the finished artificial marble product undergoes discoloration. Therefore, silver is indispensable in the vicinity of the product surface in order to exert an antibacterial effect. In order to prevent discoloration, it was better that silver was not present in the vicinity of the product surface, and it was difficult to adjust, but the silver-based antibacterial agent and the inorganic-based agent in which silver was supported on the inorganic-based support of the present invention were used. When a system auxiliary material is used, elution of silver can be suppressed, discoloration of the product can be prevented, and a product having excellent physical properties and appearance over a long period with little deterioration of light resistance due to ultraviolet rays can be obtained.

[Brief description of the drawings]

FIG. 1 is a molding apparatus and a manufacturing process for producing a compressed resin sheet of the present invention.

FIG. 2 is a molding apparatus and a manufacturing process for producing the antibacterial artificial marble product of the present invention.

FIG. 3 shows an antibacterial effect.

FIG. 4 is a diagram showing a color difference effect.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Forming apparatus 2 ... Belt conveyor 3 ... 1st resin hopper 3a, 3b ... Supply pipe 4 ... Reinforcement supply hopper 5 ... Cutter 6a, 6b ... Impregnation roll 7 ... Scraping roll 8 ... 1st polyethylene film supply apparatus 8a ... First polyethylene film 8b Roll fixing device 8c Transport roller 8d Inclined plate 9 Second polyethylene film supply device 9a Second polyethylene film 9b Roll fixing device 9c First transport roller 9d Second transport roller 10 Winding device 11: Pressing device 14: Compressed resin sheet 20: Antibacterial artificial marble product 21: Upper mold 22: Lower mold A: Antibacterial agent B: Silver-based antibacterial agent C: Resin paste

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI B29K 105: 06 105: 16 C04B 111: 54

Claims (13)

[Claims] 1. An antibacterial artificial marble characterized in that the antibacterial agent is dispersed throughout the artificial marble product and that a large amount of the antibacterial agent is aggregated near the surface layer side. 2. An antibacterial artificial marble characterized in that the antibacterial agent and the inorganic auxiliary material are dispersed throughout the artificial marble product and that a large amount of the antimicrobial agent and inorganic auxiliary material are aggregated near the surface layer side. 3. The antibacterial agent includes silver ion, silver complex salt, silver complex ion, silver nitrate, silver sulfate, silver lactate, silver chlorate, silver fluoride, silver picoxonate, silver phosphate, silver phosphite. The antibacterial artificial marble according to claim 1, wherein the antibacterial artificial marble is a silver compound such as a silver salt or a silver-based antibacterial agent such as a water-soluble glass containing silver oxide in a component. 4. The silver-based antibacterial agent is characterized in that at least one of the silver compound and water-soluble glass containing silver oxide in a component is supported on the surface of an inorganic carrier. 3. The antibacterial artificial marble according to 3. 5. The antibacterial artificial marble according to claim 4, wherein the inorganic carrier is an ion-exchange or dissolution carrier. 6. The antibacterial artificial marble according to claim 2, wherein the inorganic auxiliary material is an ion-exchange or dissolution-type carrier. 7. The addition amount of the antibacterial agent or silver-based antibacterial agent and the inorganic auxiliary material is 0.1 to 5.0% of the whole main material.
The antibacterial artificial marble according to any one of claims 1 to 5, wherein the content is part by weight. 8. The addition amount of the antibacterial agent or the silver-based antibacterial agent is 0.1 to 5.0% by weight of the whole, and the combination of the antibacterial agent or the silver-based antibacterial agent and the inorganic auxiliary material. 7. The antibacterial artificial marble according to claim 6, wherein the ratio is from 9: 1 to 6: 4. 9. The antibacterial artificial marble according to claim 1, wherein the artificial marble mainly comprises a synthetic resin and a filler. 10. The antibacterial artificial marble according to claim 1, wherein the antibacterial artificial marble contains a reinforcing material. 11. An antibacterial agent or an antibacterial agent and an inorganic auxiliary material are mixed and stirred in a resin material, and then a filler and the like are added thereto. A method for producing antibacterial artificial marble, comprising heating and pressurizing after being placed in a mold. 12. The method for producing antibacterial artificial marble according to claim 11, wherein a reinforcing material is added to and mixed with the resin paste. 13. The method for producing an antibacterial artificial marble according to claim 11, wherein the heating is performed with a temperature difference between the upper mold and the lower mold.