JPH111380A - Production of antimicrobial ceramic product - Google Patents
Production of antimicrobial ceramic productInfo
- Publication number
- JPH111380A JPH111380A JP17316297A JP17316297A JPH111380A JP H111380 A JPH111380 A JP H111380A JP 17316297 A JP17316297 A JP 17316297A JP 17316297 A JP17316297 A JP 17316297A JP H111380 A JPH111380 A JP H111380A
- Authority
- JP
- Japan
- Prior art keywords
- antibacterial
- glaze
- layer
- silver
- antibacterial agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 230000000845 anti-microbial effect Effects 0.000 title abstract description 7
- 229910052709 silver Inorganic materials 0.000 claims abstract description 30
- 239000004332 silver Substances 0.000 claims abstract description 30
- 238000010304 firing Methods 0.000 claims abstract description 9
- 239000003242 anti bacterial agent Substances 0.000 claims description 67
- 230000000844 anti-bacterial effect Effects 0.000 claims description 52
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 7
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 229940100890 silver compound Drugs 0.000 claims description 4
- 150000003379 silver compounds Chemical class 0.000 claims description 4
- 229910000161 silver phosphate Inorganic materials 0.000 claims description 4
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 claims description 4
- 229940019931 silver phosphate Drugs 0.000 claims description 4
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052573 porcelain Inorganic materials 0.000 claims description 3
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 3
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 229910001923 silver oxide Inorganic materials 0.000 claims description 3
- 239000004599 antimicrobial Substances 0.000 abstract description 14
- 238000002845 discoloration Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 229910010293 ceramic material Inorganic materials 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 230000005012 migration Effects 0.000 abstract 1
- 238000013508 migration Methods 0.000 abstract 1
- 230000008022 sublimation Effects 0.000 abstract 1
- 238000000859 sublimation Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 51
- 230000001580 bacterial effect Effects 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002344 surface layer Substances 0.000 description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 4
- 235000011941 Tilia x europaea Nutrition 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 239000004571 lime Substances 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 239000010433 feldspar Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 235000014692 zinc oxide Nutrition 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- -1 water-soluble glass Chemical compound 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052845 zircon Inorganic materials 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical group 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/67—Biocides
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は施釉陶磁器品の製
造方法に関し、詳しくは抗菌性を有する施釉陶磁器品の
製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a glazed ceramic article, and more particularly to a method for producing a glazed ceramic article having antibacterial properties.
【０００２】[0002]
【従来の技術】従来、陶磁器品に抗菌性を付与する手段
として、陶磁器素地の表面に釉薬層を施し、そしてその
釉薬層の更に表面に抗菌剤の層を施した上でこれを焼成
する方法、或いは釉薬中に予め抗菌剤を含有させてお
き、これを陶磁器素地の上側に施して焼成する方法等が
知られている。2. Description of the Related Art Conventionally, as a means of imparting antibacterial properties to a ceramic article, a method of applying a glaze layer to the surface of a ceramic body, applying an antibacterial agent layer to the surface of the glaze layer, and firing the same. Alternatively, there is known a method in which an antibacterial agent is previously contained in a glaze, applied to the upper side of a ceramic body, and fired.
【０００３】陶磁器品に抗菌性を持たせる理由は、陶磁
器品表面での菌の増殖を抑制して陶磁器品表面を清浄に
保つためであり、このことからすれば、上記方法は何れ
も陶磁器品の最表層に抗菌剤の層を施すか又は最表層を
構成する材料中に予め抗菌剤を含有させておくものであ
り、合理的であると言える。[0003] The reason for imparting antibacterial properties to a ceramic article is to keep the surface of the ceramic article clean by suppressing the growth of bacteria on the surface of the ceramic article. It is reasonable to apply an antibacterial agent layer to the outermost layer of the above or to preliminarily contain the antibacterial agent in a material constituting the outermost layer.
【０００４】ところで抗菌剤の種類には従来種々のもの
が知られているが、大別すると有機系の抗菌剤と無機系
の抗菌剤とに分けることができる。而して有機系の抗菌
剤は耐熱性が低く、耐久性が劣る問題があり、そこで陶
磁器品用の抗菌剤としては耐熱性に優れ、また広い抗菌
スペクトルを有して、種々の菌に対して抗菌性を発揮す
る無機系の抗菌剤が用いられている。Various kinds of antibacterial agents are conventionally known, but they can be roughly classified into organic antibacterial agents and inorganic antibacterial agents. Therefore, organic antibacterial agents have a problem that heat resistance is low and durability is inferior.Therefore, as an antibacterial agent for ceramic products, it has excellent heat resistance and has a wide antibacterial spectrum, and it has various antibacterial properties. Inorganic antibacterial agents exhibiting antibacterial properties are used.
【０００５】無機系の抗菌剤の場合、ゼオライト，リン
酸カルシウム，リン酸ジルコニウム，シリカゲル，水溶
性ガラス，チタニア等の無機酸化物を担体として、その
担体に銀，銅，亜鉛等の抗菌成分を担持させたもの（担
持の形態にはイオン交換，吸着，固溶，ガラス成分とし
ての担持等各種形態がある）が一般的であり、中でも抗
菌成分として銀を担持させたものが専ら用いられている
（銀が最も抗菌効果が高く、安全性も高い）。或いはま
たこのような担体に抗菌成分を担持させず、金属銀や銀
化合物をそのまま抗菌剤として用いることも行われてい
る。In the case of an inorganic antibacterial agent, an inorganic oxide such as zeolite, calcium phosphate, zirconium phosphate, silica gel, water-soluble glass, titania is used as a carrier, and an antibacterial component such as silver, copper, zinc or the like is carried on the carrier. (A variety of forms such as ion exchange, adsorption, solid solution, and support as a glass component) are generally used. Among them, those carrying silver as an antibacterial component are exclusively used ( Silver has the highest antibacterial effect and the highest safety.) Alternatively, such a carrier does not carry an antibacterial component, and metallic silver or a silver compound is directly used as an antibacterial agent.
【０００６】[0006]
【発明が解決しようとする課題】しかしながらこのよう
な銀を抗菌成分とする抗菌剤の層を、上記のように陶磁
器品の釉薬層の表面に施したり、或いは釉薬中に予め抗
菌剤を含有させて陶磁器素地の表面に施した状態で焼成
するようにした場合、以下のような問題を生じる。即
ち、抗菌剤の層が陶磁器品の最表層にのみ存在すること
となるため、表層の減耗により抗菌剤が減少して抗菌能
力が経時的に低下したり無くなったりする問題があり、
或いは陶磁器品の製造工程でハンドリング中に表面層が
剥がれたりすると、同じく抗菌能力が低下したり、無く
なったりする問題が生じる。However, such a layer of antibacterial agent containing silver as an antibacterial component is applied to the surface of the glaze layer of ceramics as described above, or the antibacterial agent is previously contained in the glaze. In the case where firing is performed on the surface of the ceramic body, the following problems occur. That is, since the layer of the antibacterial agent is present only in the outermost layer of the ceramic article, there is a problem that the antibacterial agent decreases due to the wear of the surface layer, and the antibacterial ability decreases or disappears with time.
Alternatively, if the surface layer is peeled off during handling in the process of manufacturing a ceramic article, there is a problem that the antibacterial ability is also reduced or lost.
【０００７】更には銀を抗菌成分とする抗菌剤の場合、
焼成中に銀が気散・蒸発して一部失われてしまう問題が
あり、この場合にも抗菌能力が低下する問題を生じる。Further, in the case of an antibacterial agent containing silver as an antibacterial component,
There is a problem that silver is diffused and evaporated during firing, and a part of the silver is lost. In this case, there is also a problem that the antibacterial ability is reduced.
【０００８】加えて銀を抗菌成分とする抗菌剤を用い
て、これを最表層の釉薬層の表面に施し或いは釉薬中に
含有させて施し、その後焼成した場合、銀の存在に起因
して表面が黄色に発色したり色むらを生じたりし、陶磁
器品の外観品質を低下させるといった困難な問題を生じ
る。[0008] In addition, when an antibacterial agent containing silver as an antibacterial component is applied to the surface of the outermost glaze layer or contained in the glaze and then fired, if the surface is baked, the surface will be lost due to the presence of silver. However, there are difficult problems such as the formation of yellow or uneven color, and the deterioration of appearance quality of ceramic articles.
【０００９】更に釉薬中に銀を抗菌成分とする抗菌剤を
含有させるようにした場合、抗菌成分が釉薬の泥漿中に
微量に溶出して釉薬泥漿の粘度を変化させるため確実な
粘度調整を行わなければならず、しかも抗菌成分として
の銀が釉薬設備の金属部品を侵したり、銀が析出して塊
となり、これが釉薬中に混じると異物となって釉薬層に
ピンホールを発生させる原因となるなど各種の弊害を生
じる問題がある。Further, when an antibacterial agent containing silver as an antibacterial component is contained in the glaze, a certain amount of the antibacterial component is eluted into the glaze slurry to change the viscosity of the glaze slurry. In addition, silver as an antibacterial component attacks metal parts of the glaze equipment, and silver precipitates and forms a lump, which when mixed in the glaze becomes a foreign substance and causes pinholes in the glaze layer And other problems.
【００１０】[0010]
【課題を解決するための手段】本願の発明はこのような
課題を解決するために案出されたものである。而して請
求項１の抗菌性陶磁器品の製造方法は、陶磁器素地の表
面上に釉薬を層状に施し、焼成することにより施釉陶磁
器品を得るに際して、最表層の釉薬層の下側且つ該陶磁
器素地の表面上に、銀を抗菌成分とする抗菌剤を層状に
施し、その状態で前記焼成を行うことを特徴とする。Means for Solving the Problems The present invention has been devised to solve such problems. In the method for producing an antibacterial ceramic article according to claim 1, a glaze is applied in layers on the surface of the ceramic base and fired to obtain a glazed ceramic article, the lower side of the outermost glaze layer and the ceramic. An antimicrobial agent containing silver as an antimicrobial component is applied in a layer on the surface of the substrate, and the baking is performed in that state.
【００１１】請求項２の抗菌性陶磁器品の製造方法は、
請求項１において、前記陶磁器素地の表面上に直接前記
抗菌剤を釉薬と非混合状態で単独に層状に施し、該抗菌
剤の層の上側に最表層の釉薬層を施して焼成することを
特徴とする。[0011] The method for producing an antibacterial ceramic article according to claim 2 comprises:
2. The method according to claim 1, wherein the antibacterial agent is applied directly to the surface of the ceramic body in a layered state without being mixed with glaze, and the outermost glaze layer is applied above the antibacterial agent and fired. And
【００１２】請求項３の抗菌性陶磁器品の製造方法は、
請求項２において、前記抗菌剤をスラリー状態で前記陶
磁器素地の表面上に塗布することによって、前記抗菌剤
の層を施すことを特徴とする。[0012] The method for producing an antibacterial ceramic article according to claim 3 comprises:
The method according to claim 2, wherein the layer of the antibacterial agent is applied by applying the antibacterial agent in a slurry state on the surface of the ceramic body.
【００１３】請求項４の抗菌性陶磁器品の製造方法は、
請求項１において、前記陶磁器素地の表面上に第一の釉
薬層を施した上で、その上側に前記最表層の釉薬層を第
二の釉薬層として施し、該第一の釉薬中に前記抗菌剤を
含有させることで、前記最表層の釉薬層の下側に前記抗
菌剤の層を形成することを特徴とする。[0013] The method for producing an antibacterial ceramic article according to claim 4 comprises:
2. The method according to claim 1, wherein a first glaze layer is provided on the surface of the ceramic body, and the uppermost glaze layer is provided thereon as a second glaze layer, and the antibacterial agent is contained in the first glaze. By containing an agent, the antibacterial agent layer is formed below the outermost glaze layer.
【００１４】請求項５の抗菌性陶磁器品の製造方法は、
請求項１〜４の何れかにおいて、前記抗菌剤として金属
銀若しくは酸化銀，硝酸銀，リン酸銀，炭酸銀等の銀化
合物を担体に担持させない形態で用いることを特徴とす
る。[0014] The method for producing an antibacterial ceramic article according to claim 5 is as follows.
The method according to any one of claims 1 to 4, wherein the antibacterial agent is a metal compound or a silver compound such as silver oxide, silver nitrate, silver phosphate, silver carbonate or the like which is not supported on a carrier.
【００１５】[0015]
【作用及び発明の効果】上記のように請求項１の製造方
法は、最表層の釉薬層の下側且つ陶磁器素地の表面上
に、銀を抗菌成分とする抗菌剤を層状に施し、その状態
で焼成を行うものである。As described above, according to the manufacturing method of the first aspect, an antibacterial agent containing silver as an antibacterial component is applied in a layer on the lower side of the outermost glaze layer and on the surface of the ceramic body. The baking is performed.
【００１６】本発明者は、当初、施釉陶磁器品の表面に
抗菌性を持たせるためには、最表層の釉薬層の表面に抗
菌剤の層を施すか又は少なくとも最表層の釉薬層中に抗
菌剤を含有させておくことが必要であるものと考えてい
た。しかしながらこのようにした場合各種の問題を生じ
ることは前述した通りである。At first, the inventor of the present invention provided an antibacterial agent on the surface of the outermost glaze layer or provided at least an antibacterial agent in the outermost glaze layer in order to impart antibacterial properties to the surface of the glazed ceramic article. It was thought that it was necessary to contain the agent. However, as described above, various problems occur in this case.
【００１７】しかるに最表層の釉薬層の下側に抗菌剤の
層を施した状態で焼成を行った場合にも抗菌性を発現す
ることが判明した。これは次の理由に基づくものと考え
られる。即ち最表層の釉薬層の下側に抗菌剤の層を施し
た場合であっても、その後の焼成時に溶融した釉薬中に
抗菌剤が均一に拡散して表面まで達し、抗菌作用を発揮
するものと考えられる。However, it has been found that antibacterial properties are exhibited also when baking is performed in a state in which an antibacterial agent layer is provided below the outermost glaze layer. This is considered to be based on the following reasons. In other words, even when a layer of antibacterial agent is applied under the outermost glaze layer, the antibacterial agent diffuses uniformly into the glaze melted during subsequent firing and reaches the surface, exhibiting antibacterial action. it is conceivable that.
【００１８】本発明の製造方法により得られる施釉陶磁
器品の場合、表面部位に抗菌剤が集中して多く存在する
といったことがないため、表層が減耗しても抗菌能力が
低下又は消失することはなく、また表層に銀が集中して
多く存在することに起因して黄色等の発色を起こしたり
色むらを起こしたりして、陶磁器品の外観品質を低下さ
せるといった問題も解決することができる。In the case of a glazed ceramic article obtained by the production method of the present invention, since the antibacterial agent is not concentrated and present on the surface portion, the antibacterial ability is not reduced or lost even if the surface layer is worn out. In addition, it is possible to solve the problem of causing color development such as yellow or uneven color due to the presence of a large amount of silver concentrated on the surface layer, thereby deteriorating the appearance quality of the ceramic article.
【００１９】更に最表層の釉薬層の下側に抗菌剤を層状
に施した状態で焼成を行うことから、焼成の際に抗菌成
分である銀が表面から気散・蒸発する現象を効果的に抑
制することができ、ひいては抗菌剤の量を少なくするこ
とができ、抗菌剤に要するコストを低減することが可能
となる。Further, since the baking is performed in a state in which the antibacterial agent is applied in a layer below the outermost glaze layer, the phenomenon that silver as an antibacterial component diffuses and evaporates from the surface during the baking is effectively prevented. Thus, the amount of the antibacterial agent can be reduced, and the cost required for the antibacterial agent can be reduced.
【００２０】また施釉陶磁器品の製造工程におけるハン
ドリング中に表層部の剥がれ等によって抗菌剤が失われ
るといった問題も解決できる。Further, it is possible to solve the problem that the antibacterial agent is lost due to peeling of the surface layer during handling in the manufacturing process of the glazed ceramic article.
【００２１】尚、本発明において銀を抗菌成分とする抗
菌剤を用いる理由は次の点にある。即ち、銀を抗菌成分
とする抗菌剤が上記のように最も抗菌効果が高く、また
安全性が高いことに加えて、例えば銅を抗菌成分とする
抗菌剤の場合、銀を抗菌成分とするものに比べて焼成時
に発色の程度が大きく、更に亜鉛を抗菌成分とする抗菌
剤の場合には抗菌効果そのものが不十分であることによ
る。The reason for using an antibacterial agent containing silver as an antibacterial component in the present invention is as follows. That is, an antibacterial agent containing silver as an antibacterial component has the highest antibacterial effect as described above, and in addition to having high safety, for example, in the case of an antibacterial agent containing copper as an antibacterial component, silver is used as an antibacterial component This is because the degree of color development at the time of baking is greater than that of baking, and in the case of an antibacterial agent containing zinc as an antibacterial component, the antibacterial effect itself is insufficient.
【００２２】本発明は各種の陶磁器品を製造するに際し
て適用可能なものである。例えばタイルの製造に際して
適用することも可能であるし、或いは便器，洗面器等の
衛生陶器を製造するに際して適用することも勿論可能で
ある。その他種々の陶磁器品の製造に適用可能である。The present invention is applicable when manufacturing various ceramic articles. For example, the present invention can be applied to the manufacture of tiles, or of course to the manufacture of sanitary ware such as toilets and washbasins. It can be applied to the manufacture of various other ceramics.
【００２３】またタイル製造に適用する場合には、仮焼
きしたタイル素地の表面上に抗菌剤を層状に施すように
しても良いし、或いは成形後乾燥した生素地状態の陶磁
器素地の表面上に抗菌剤を層状に施すようにしても良
い。一方便器，洗面器等の衛生陶器の場合、一般には成
形し乾燥した生素地状態の陶磁器素地の表面上に抗菌剤
を層状に施すこととなる。When applied to the production of tiles, an antimicrobial agent may be applied in layers on the surface of the calcined tile base, or may be applied on the surface of the ceramic base in a green base state after being formed and dried. The antimicrobial agent may be applied in layers. On the other hand, in the case of sanitary ware such as a toilet bowl and a wash basin, an antibacterial agent is generally applied in a layered form on the surface of a molded and dried green body.
【００２４】本発明においては、陶磁器素地の表面上に
直接抗菌剤を釉薬と非混合状態で単独に層状に施し、そ
の抗菌剤の層の上側に最表層の釉薬層を施して焼成する
ようになすことができる（請求項２）。このようにした
場合、最表層の釉薬層の下側に施した抗菌剤が焼成時に
釉薬の溶融に伴って表面部まで拡散移動してきて抗菌効
果を発揮する。In the present invention, the antibacterial agent is applied directly on the surface of the ceramic body in a layer without being mixed with the glaze, and the outermost glaze layer is applied on the upper side of the antibacterial agent and fired. (Claim 2). In this case, the antibacterial agent applied to the lower side of the outermost glaze layer diffuses and moves to the surface with the melting of the glaze during firing, thereby exhibiting the antibacterial effect.
【００２５】この請求項２の方法では、抗菌剤を釉薬中
に含有させることなく単独で陶磁器素地の表面上に施す
ようにしていることから、抗菌剤を釉薬中に含有させる
ことに起因して生じる上記問題、即ち抗菌成分である銀
が釉薬設備の金属部品を腐食したり、或いは銀が析出し
てその塊が釉薬中に混じり込み、異物となってピンホー
ル等を発生させる原因となるなどの問題を解決すること
ができる。In the method of claim 2, since the antibacterial agent is applied to the surface of the ceramic body alone without being contained in the glaze, the antibacterial agent is contained in the glaze. The above-mentioned problems that occur, that is, silver, which is an antibacterial component, corrodes metal parts of the glaze equipment, or silver precipitates out and the lump mixes into the glaze, causing foreign matter to generate pinholes and the like. Problem can be solved.
【００２６】この場合において、抗菌剤をスラリー状態
で陶磁器素地の表面上に塗布することで抗菌剤の層を施
すようになすことができる（請求項３）。このようにす
ることによって、容易に陶磁器素地の表面上に抗菌剤の
層を施すことができる。In this case, the antimicrobial agent can be applied by applying the antimicrobial agent in a slurry state on the surface of the ceramic body (claim 3). By doing so, a layer of the antibacterial agent can be easily applied on the surface of the ceramic body.
【００２７】本発明においては、また、最表層の釉薬層
を第二の釉薬層としてその下側に第一の釉薬層を施し、
そしてその第一の釉薬中に抗菌剤を含有させるようにな
すこともできる（請求項４）。このようにした場合に
も、第一の釉薬中に含有されている抗菌剤が焼成の際に
表面まで拡散移動してきて抗菌効果を発揮する。In the present invention, the outermost glaze layer is used as a second glaze layer, and the first glaze layer is formed below the second glaze layer.
An antimicrobial agent can be contained in the first glaze (claim 4). Also in this case, the antibacterial agent contained in the first glaze diffuses and moves to the surface during firing and exhibits an antibacterial effect.
【００２８】本発明においては、抗菌成分である銀を前
述したような各種担体に担持させた形態で用いることも
可能であるが、金属銀若しくは酸化銀，硝酸銀，リン酸
銀，炭酸銀等の銀化合物の形態で且つこれを担体に担持
させない形態で用いることができる（請求項５）。この
ような形態で抗菌剤を用いた場合、焼成に際して有効に
抗菌剤を最表層の釉薬の層内で拡散させて表面に移行さ
せることができる。In the present invention, silver, which is an antibacterial component, can be used in the form of being supported on the above-mentioned various carriers, but it is possible to use metallic silver or silver oxide, silver nitrate, silver phosphate, silver carbonate or the like. It can be used in the form of a silver compound and not supported on a carrier (claim 5). When the antibacterial agent is used in such a form, the antibacterial agent can be effectively diffused in the outermost glaze layer and transferred to the surface during baking.
【００２９】[0029]
【実施例】次に本発明の実施例を以下に詳述する。 〈実施例１〉下記原料組成の陶磁器素地（図１参照。こ
の例ではタイル素地１０） 蝋石：４８％ 粘土：４０％ 石灰：１２％ （但し調合比率は重量％） の素焼き品表面に抗菌剤スラリーをスプレー塗布して抗
菌剤層１２を施し、更にその上側に下記の原料組成の釉
薬 長石：５２％ 石灰：１２％ 珪砂：１２％ 粘土： ７％ 亜鉛華：５％ フリット：１２％ ジルコン：１０％（外添加） を８ｇ／１００ｃｍ2の量で施して釉薬層１４を形成
し、これをローラーハースキルン（ＲＨＫ）で焼成した
（焼成条件は１１４０℃，２３分）。そして得られた焼
成品について表１に示す各種評価を行った。Next, embodiments of the present invention will be described in detail. <Example 1> A ceramic body having the following raw material composition (see Fig. 1; tile body 10 in this example) Roseki: 48% Clay: 40% Lime: 12% (However, the mixing ratio is wt%) The antibacterial agent layer 12 is applied by spraying the slurry, and a glaze having the following raw material composition is further provided thereon: Feldspar: 52% Lime: 12% Silica: 12% Clay: 7% Zinc white: 5% Frit: 12% Zircon: 10% (external addition) was applied in an amount of 8 g / 100 cm 2 to form the glaze layer 14, which was fired by a roller hearth kiln (RHK) (firing conditions: 1140 ° C., 23 minutes). Various evaluations shown in Table 1 were performed on the obtained fired product.
【００３０】[0030]
【表１】 [Table 1]
【００３１】尚、抗菌剤スラリーは下記の組成とし、こ
れを０．５ｇ／１００ｃｍ2の量でタイル素地１０表面
に施した。 リン酸銀：５０％ 水 ：５０％ 添加剤 ：２％（分散剤）The antibacterial agent slurry had the following composition, and was applied to the surface of the tile substrate 10 in an amount of 0.5 g / 100 cm 2 . Silver phosphate: 50% Water: 50% Additive: 2% (dispersant)
【００３２】但し表１中ΔＥ測定用のものについては抗
菌剤を通常の３倍量用いた。However, the antibacterial agent used in Table 1 was used in an amount of ΔE which was three times the usual amount.
【００３３】ここで減菌率は ｛（無抗菌タイル生菌数−抗菌タイル生菌数）／無抗菌
タイル生菌数｝×１００（％） であって、この測定は以下の条件で行った。 １．菌液の調製 普通ブイヨン培地で３５℃，一夜振とう培養した試験菌
（大腸菌又は黄色ブドウ球菌）の培養液を滅菌リン酸緩
衝液で約１００００倍に希釈し、菌液とした。その菌液
をシャーレに滴下し、生菌数を測定した。 ２．試験操作 試料表面に菌液１ミリリットルを滴下後、４．５×４．
５ｃｍの滅菌ポリエチレンシートを載せて２５℃で２４
時間放置した。尚、菌液をシャーレに滴下したものを対
照試料とし、同様に試験した。 ３．減菌率の測定 上記２４時間放置後の生菌数を以下の方法で測定した。
即ち試料表面をＳＣＤＬＰ培地（日本製薬）１０ミリリ
ットルで洗い出し、その洗い出し液について標準寒天培
地を用いた混釈平板培養法（３５℃，２日間培養）で培
養し、生菌数を測定した。そしてその２４時間放置後の
無抗菌タイルと抗菌タイルの測定生菌数から減菌率を求
めた。また表１中のΔＥは変色の程度（色差）を示すも
ので、ＪＩＳ Ｚ ８７３０に準拠するものである。更に
表１中のＡｇ量は、蛍光Ｘ線により求めたもので高い数
字ほどＡｇ残量が多いことを示す。Here, the sterilization rate was {(viable cell count of non-bacterial antibacterial tile−number of viable cell of antibacterial tile) / viable cell count of non-bacterial tile} × 100 (%). This measurement was performed under the following conditions. . 1. Preparation of Bacterial Solution A culture solution of a test bacterium (Escherichia coli or Staphylococcus aureus) cultured with shaking at 35 ° C. overnight in a normal bouillon medium was diluted about 10,000 times with a sterilized phosphate buffer to obtain a bacterial solution. The bacterial solution was dropped on a petri dish, and the number of viable bacteria was measured. 2. Test operation After dropping 1 ml of the bacterial solution on the sample surface, 4.5 × 4.
Place a 5cm sterile polyethylene sheet at 25 ° C for 24 hours.
Left for hours. The same test was carried out by using a drop of the bacterial solution on a petri dish as a control sample. 3. Measurement of sterilization rate The number of viable bacteria after standing for 24 hours was measured by the following method.
That is, the sample surface was washed out with 10 ml of SCDLP medium (Nihon Pharmaceutical), and the washed out liquid was cultured by a pour plate method (cultured at 35 ° C. for 2 days) using a standard agar medium, and the number of viable bacteria was measured. Then, the sterilization rate was determined from the measured viable cell counts of the non-bacterial tile and the antibacterial tile after standing for 24 hours. Further, ΔE in Table 1 indicates the degree of discoloration (color difference) and conforms to JIS Z 8730. Further, the Ag amount in Table 1 was obtained by X-ray fluorescence, and the higher the number, the higher the amount of Ag remaining.
【００３４】〈実施例２〉タイル素地１０の表面に上記
抗菌剤を含有させた第一の釉薬を、抗菌剤量が上記量と
なるように層状に施して第一の釉薬層（抗菌剤層）を形
成し、更にその上側に第二の釉薬層（最表層の釉薬層）
を施し、これを実施例１と同様の条件で焼成した。そし
てその焼成品について実施例１と同様の評価を行った。Example 2 A first glaze containing the above-mentioned antibacterial agent was applied on the surface of the tile base 10 in a layered manner so that the amount of the antibacterial agent became the above-mentioned amount. ), And a second glaze layer (the outermost glaze layer) on the upper side
And fired under the same conditions as in Example 1. Then, the same evaluation as in Example 1 was performed on the fired product.
【００３５】尚、この実施例２において第一の釉薬とし
ては下記組成 長石：５０％ 珪石： ８％ 石灰：１１％ 粘土： ６％ フリット：１５％ ジルコン： ８％ 亜鉛華： ２％ のものを、また第二の釉薬として下記の組成 長石：６０％ 珪石：１０％ 石灰：１２％ 粘土： ８％ 亜鉛華：１０％ のものをそれぞれ用いた。施釉量は、第一の釉薬につい
ては６ｇ／１００ｃｍ2、第二の釉薬については４ｇ／
１００ｃｍ2とした。The first glaze in Example 2 had the following composition: Feldspar: 50% Silica: 8% Lime: 11% Clay: 6% Frit: 15% Zircon: 8% Zinc white: 2% The second glaze used had the following composition: feldspar: 60% silica: 10% lime: 12% clay: 8% zinc white: 10% The amount of glaze is 6 g / 100 cm 2 for the first glaze and 4 g / 100 g for the second glaze.
It was 100 cm 2 .
【００３６】結果が表１に併せて示してある。これらの
結果から、本発明に従って抗菌剤の層を施し、焼成した
場合においても良好な抗菌効果の得られること、また最
表層部の変色の程度が小さいことが分かる。The results are shown in Table 1. From these results, it can be seen that a good antibacterial effect can be obtained even when the antibacterial agent layer is applied according to the present invention and baked, and that the degree of discoloration of the outermost layer is small.
【００３７】以上本発明の実施例を詳述したがこれはあ
くまで一例示であり、本発明は上例以外の、種々の抗菌
性を有する施釉陶磁器品を製造するに際して適用可能で
あるなど、その主旨を逸脱しない範囲において様々な変
更を加えた態様で実施可能である。Although the embodiment of the present invention has been described in detail above, this is merely an example, and the present invention is applicable to the production of glazed ceramic articles having various antibacterial properties other than the above examples. The present invention can be implemented in various modified forms without departing from the scope of the invention.
【図１】本発明の一実施例の説明図である。FIG. 1 is an explanatory diagram of one embodiment of the present invention.
１０ タイル素地（陶磁器素地） １２ 抗菌剤層 １４ 釉薬層 10 tile body (porcelain body) 12 antibacterial agent layer 14 glaze layer
Claims (5)
し、焼成することにより施釉陶磁器品を得るに際して最
表層の釉薬層の下側且つ該陶磁器素地の表面上に、銀を
抗菌成分とする抗菌剤を層状に施し、その状態で前記焼
成を行うことを特徴とする抗菌性陶磁器品の製造方法。1. When glaze is applied in layers on the surface of a ceramic body and fired to obtain a glazed ceramic article, silver is used as an antibacterial component under the glaze layer on the outermost layer and on the surface of the ceramic body. A method for producing an antibacterial porcelain article, comprising applying an antibacterial agent in a layered form and performing the baking in that state.
面上に直接前記抗菌剤を釉薬と非混合状態で単独に層状
に施し、該抗菌剤の層の上側に最表層の釉薬層を施して
焼成することを特徴とする抗菌性陶磁器品の製造方法。2. The method according to claim 1, wherein the antibacterial agent is applied directly on the surface of the ceramic body in a layer without being mixed with the glaze, and an outermost glaze layer is applied above the antibacterial agent layer. A method for producing an antibacterial porcelain article characterized by firing.
ー状態で前記陶磁器素地の表面上に塗布することによっ
て、前記抗菌剤の層を施すことを特徴とする抗菌性陶磁
器品の製造方法。3. The method for manufacturing an antibacterial ceramic article according to claim 2, wherein the antibacterial agent is applied by applying the antibacterial agent in a slurry state on the surface of the ceramic body.
面上に第一の釉薬層を施した上で、その上側に前記最表
層の釉薬層を第二の釉薬層として施し、該第一の釉薬中
に前記抗菌剤を含有させることで、前記最表層の釉薬層
の下側に前記抗菌剤の層を形成することを特徴とする抗
菌性陶磁器品の製造方法。4. The method according to claim 1, wherein a first glaze layer is provided on the surface of the ceramic body, and the outermost glaze layer is provided thereon as a second glaze layer. A method for producing an antibacterial ceramic article, wherein the antibacterial agent is contained in the glaze to form a layer of the antibacterial agent below the outermost glaze layer.
菌剤として金属銀若しくは酸化銀，硝酸銀，リン酸銀，
炭酸銀等の銀化合物を担体に担持させない形態で用いる
ことを特徴とする抗菌性陶磁器品の製造方法。5. The antibacterial agent according to claim 1, wherein the antibacterial agent is metallic silver or silver oxide, silver nitrate, silver phosphate,
A method for producing an antibacterial ceramic article, wherein a silver compound such as silver carbonate is not supported on a carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17316297A JP3398016B2 (en) | 1997-06-13 | 1997-06-13 | Manufacturing method of antibacterial ceramics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17316297A JP3398016B2 (en) | 1997-06-13 | 1997-06-13 | Manufacturing method of antibacterial ceramics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH111380A true JPH111380A (en) | 1999-01-06 |
| JP3398016B2 JP3398016B2 (en) | 2003-04-21 |
Family
ID=15955258
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17316297A Expired - Lifetime JP3398016B2 (en) | 1997-06-13 | 1997-06-13 | Manufacturing method of antibacterial ceramics |
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| Country | Link |
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| KR100411950B1 (en) * | 2001-09-12 | 2003-12-18 | 신홍대 | Method of silver plating on the tile |
| KR100443035B1 (en) * | 2002-01-12 | 2004-08-04 | 신홍대 | Precious metals-jewel tile and the manufacturing method of the same |
| KR100689632B1 (en) * | 2005-02-01 | 2007-03-09 | 주식회사 골든벨금속 | Household pottery using silver nano and manufacturing method |
| WO2010126917A1 (en) * | 2009-04-27 | 2010-11-04 | Microban Products Company | Ceramic glazing composition having antimicrobial property |
| EP2118038A4 (en) * | 2007-02-20 | 2015-11-04 | Microban Products | CERAMIC ENAMEL WITH ANTIMICROBIAL PROPERTY |
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1997
- 1997-06-13 JP JP17316297A patent/JP3398016B2/en not_active Expired - Lifetime
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