CN1389436A - Sanitary ware with nano self-cleaning enamel and its making process - Google Patents

Sanitary ware with nano self-cleaning enamel and its making process Download PDF

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Publication number
CN1389436A
CN1389436A CN 02125311 CN02125311A CN1389436A CN 1389436 A CN1389436 A CN 1389436A CN 02125311 CN02125311 CN 02125311 CN 02125311 A CN02125311 A CN 02125311A CN 1389436 A CN1389436 A CN 1389436A
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China
Prior art keywords
coat enamel
cover
sanitary ware
ground
glaze
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Granted
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CN 02125311
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Chinese (zh)
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CN100357228C (en
Inventor
王惠文
刘拥军
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Huida Sanitary Ware Co Ltd
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TANGSHAN HUIDA CERAMIC (GROUP) CORP Ltd
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Publication of CN1389436A publication Critical patent/CN1389436A/en
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/22—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions containing two or more distinct frits having different compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2204/00—Glasses, glazes or enamels with special properties
    • C03C2204/02—Antibacterial glass, glaze or enamel
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2205/00—Compositions applicable for the manufacture of vitreous enamels or glazes
    • C03C2205/02—Compositions applicable for the manufacture of vitreous enamels or glazes for opaque enamels or glazes

Abstract

The present invention relates to a kind of sanitary ware with nano self-cleaning glazed surface, which is characterized by that said surface glaze contains Ag2O and ZnO nano compound antibacterial agent, it is a required sanitary ware made up by adopting the processes of glazing at twice and glost firing once. Its surface glaze contains nano compound material, so that said sanitary ware possesses smooth surface and the functions of resisting dirt and resisting bacteria.

Description

A kind of have Nano self-cleaning overglaze sanitary ware and a manufacture method thereof
Technical field
The present invention relates to the porcelain sanitary ware, a kind of manufacturing technology of saying so with self-cleaning overglaze sanitary ware of antifouling and antibiosis function more truely.
Background technology
The porcelain base of general sanitary ware is not white, in order to satisfy the public's demand, produce sanitary ware white or popular color, need to use the opacifying agent and the toner that contain zirconium silicate in the glaze, therefore the particle that contains milkiness phase and crystallization phases in the glassy phase of this glaze, under electron microscope, this glaze is rough; The high temperature viscosity of especially this glaze is big, and promptly temperature flowing is poor, causes the glaze plane defect to seem coarse more, makes the antifouling and antibiosis ability of this sanitary ware.
In order to overcome the above problems, the ceramist has done many work: the one, on the goods that burnt till, by later stage thermal treatment, on glaze, form the film that one deck contains antiseptic-germicide, but this kind method not only increases technology difficulty and cost, and the antiseptic-germicide thin film stability that is applied is relatively poor and peel off easily; The 2nd, interpolation antiseptic-germicide composition such as publication number are the CN1179702A patent application on former milkiness basis, but the antiseptic-germicide additive capacity is big, and cost an arm and a leg, exist a large amount of milkiness phases and the particle and the skewness of crystallization phases in the opposing party's cover-coat enamel, cause the glaze plane defect many, and hinder the release of antiseptic-germicide composition, little to the antifouling and antibiosis ability contribution of sanitary ware.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, propose a kind of self-cleaning overglaze sanitary ware and manufacture method thereof with composite nano germicide.
Sanitary ware of the present invention are made of ceramic body (be called for short porcelain base), ground-coat enamel and the cover-coat enamel that contains composite nano germicide, are characterized in containing in the cover-coat enamel ZnO and the Ag of median size＜1 μ m 2The O Nano compound, concrete composition and weight percentage thereof are as follows:
SiO 250-70％、Al 2O 36-16％、CaO6-16％、MgO1-5％、K 2O1-5％、Na 2O1-5％、ZnO2-10％、Ag 2O0.1-3.0％。
The best group of cover-coat enamel becomes: SiO 250-65%, Al 2O 38-12%, CaO6.5-9.5%, MgO1-2%, K 2O1.5-3.5%, Na 2O1.5-3.5%, ZnO2-8%, Ag 2O0.2-1.0%.
Described cover-coat enamel composition is wanted evenly, and the surface is super level and smooth, has glass composition and composite nano germicide more than 90%.Metal ion is a crucial composition in the antiseptic-germicide, strong and weak series arrangement by its antibacterial ability is as follows: Ag＞Co＞Ni＞Al＞Zn＞Cu＞Fe＞Mn＞Sn＞Ba＞Mg＞Ca, mercury, lead have certain antibacterial ability in addition, but it is poisonous, the compound of nickel, cobalt, iron can't obtain white powder, should not make industrial material, and Ag, Cu, Zn are typical sterilization metals, the present invention selects Ag 2O and ZnO Nano compound, they are the commercially available prod.
Porcelain base of the present invention will be considered the intensity, heat of material towards property and erosion resistance, and especially the coupling between the base glaze is selected the little stupalith of high temperature loss on ignition as far as possible, to reduce the glaze plane defect.Porcelain base common chemical composition and weight percentage thereof are as follows:
SiO 260-80％、Al 2O 315-25％、CaO0.1-2.0％、MgO0.1-2.0％、K 2O0.1-3.0％、Na 2O0.1-2.0％、Fe 2O 30.1-2.0％、TiO 20.1-1.0％。
Ground-coat enamel of the present invention is made up of opacifying agent and tinting material usually, therefore must pay attention between milkiness degree and uniform coloring and the base glaze and the coupling between ground-coat enamel and the cover-coat enamel, and reduce the high temperature viscosity and the loss on ignition of glaze as far as possible, ground-coat enamel Chemical Composition commonly used and weight percentage thereof are as follows:
SiO 250-70%, Al 2O 36-12%, CaO6-12%, MgO0.5-3.5%, K 2O1-5%, Na 2O0.5-5%, ZnO3-10%, ZrO 21-12%, colorant 0.1-10%.
The manufacture method of sanitary ware of the present invention may further comprise the steps:
(1) ground-coat enamel and cover-coat enamel material water are made slurries respectively;
(2) by the spray glazing of general ceramics, the ground-coat enamel slurries with step (1) preparation spray equably on the ceramic body of Manufactured sanitary ware earlier, and its thickness is 0.2-0.7mm;
(3) the cover-coat enamel slurries with step (1) preparation spray in air dried step (2) ground-coat enamel top layer, and its thickness is 0.1-0.5mm;
(4) ceramic blank drying that sprays ground-coat enamel and cover-coat enamel to moisture content less than after 0.5%, go into kiln and once be fired into transparent Nano self-cleaning overglaze sanitary ware, its firing temperature is 1150-1200 ℃, the time is 10-20 hour.
Advantage of the present invention and effect:
Sanitary ware of the present invention are owing to contain Ag in the cover-coat enamel 2O and ZnO composite nano germicide, observe down with electron microscope, its microcosmos area is even, the surface smoothness height, the base glaze of Nano self-cleaning glaze is combined (seeing Nano self-cleaning glaze of the present invention and the common comparable situation that contains the opaque glaze of opacifying agent among Fig. 1-Fig. 6 for details), but also tool anti-soil antimicrobial function.
Description of drawings
Fig. 1 is the particle situation that contains the common opaque glaze of opacifying agent and toner;
Fig. 2 is Nano self-cleaning glaze transparent of the present invention and uniformity coefficient;
Fig. 3 is common opaque glaze surface irregularity situation;
Fig. 4 is a Nano self-cleaning glaze surface smoothness of the present invention;
Fig. 5 be the base glaze of common opaque glaze in conjunction with situation,
Fig. 6 for the base glaze of Nano self-cleaning glaze of the present invention in conjunction with situation.
Embodiment
Example 1-3
The Chemical Composition of porcelain base, ground-coat enamel and the cover-coat enamel of example 1-3 and content (by weight percentage) thereof see Table 1-3.Concrete preparation process:
Conventional glaze spraying method by ceramics, earlier the ground-coat enamel slurries that prepare are sprayed on the porcelain that is fired in advance is bad, spray the cover-coat enamel slurries that prepare then on the surface of ground-coat enamel, go into kiln after being dried to water content 0.5%, burn down at 1150-1200 ℃ and promptly obtained required finished product in 10-20 hour.Concrete preparation condition sees Table 4.
Example 4
This example is a Comparative Examples, be example 2 of the present invention is contained the product of cover-coat enamel of nanometer compound fungicide and common opaque glaze surface (it is formed and content sees Table 5) product by the evaluation of electron microscope crystalline phase, obtain Fig. 1-Fig. 6 phasor.
Illustrate that by Fig. 1, Fig. 3 and shown in Figure 5: Fig. 1 common opaque glaze contains opacifying agent and toner particles, cause the glaze uniformity coefficient poor, glaze is rough and uneven in surface, common opaque glaze surface is described Fig. 3 because high temperature viscosity is big, be that temperature flowing is poor, cause the glaze plane defect many and seem coarse, Fig. 5 illustrates that the porcelain base contains pore, and the glaze plane defect easily takes place; Illustrate that by Fig. 2, Fig. 4 and shown in Figure 6: Fig. 2 Nano self-cleaning glaze of the present invention is a transparent, good evenness, Fig. 4 illustrates cover-coat enamel smooth surface degree height of the present invention, Fig. 6 illustrates that the base glaze of Nano self-cleaning glaze of the present invention is combined.
Table 1 porcelain base materials chemistry composition (%)
Project Example 1 Example 2 Example 3
????SiO 2 ????70 ????78 ????70
????Al 2O 3 ????24 ????18 ????20
????CaO ????1 ????0.5 ????2
????MgO ????1 ????0.5 ????1
????K 2O ????2 ????1 ????3
????Na 2O ????0.5 ????1 ????1.5
????Fe 2O 3 ????1 ????0.5 ????1.5
????TiO 2 ????0.5 ????0.5 ????1
Table 2 ground-coat enamel Chemical Composition (%)
Project Example 1 Example 2 Example 3
????SiO 2 ????55 ????58 ????68
????Al 2O 3 ????10 ????8 ????7
????CaO ????10 ????7 ????6
????MgO ????3 ????2 ????1
????K 2O ????2 ????4 ????1
????Na 2O ????3 ????1 ????4
????ZnO ????8 ????8 ????4
????ZrO 2 ????8 ????9.5 ????6
Yellow material ????2 ????2.5 ????3
Table 3 cover-coat enamel Chemical Composition (%)
Project Example 1 Example 2 Example 3
????SiO 2 ????56 ????63 ????70
????Al 2O 3 ????10 ????15 ????12
????CaO ????9 ????7.5 ????8
????MgO ????1.5 ????2 ????1
????K 2O ????3.5 ????1.5 ????3
????Na 2O ????3 ????2.5 ????3
????ZnO ????6 ????8 ????2
????Ag 2O ????1 ????0.5 ????1
Table 4 preparation condition
Project Example 1 Example 2 Example 3
Ground-coat enamel thickness, mm ????0.3 ????0.7 ????0.5
Cover-coat enamel thickness, mm ????0.3 ????0.5 ????0.2
Firing temperature ℃ ????1150 ????1200 ????1180
Firing time, hour ????20 ????10 ????15
Table 5 common sanitary equipment porcelain base and cover-coat enamel Chemical Composition (%)
Project The porcelain base Common glaze
????SiO 2 ????70 ????60
????Al 2O 3 ????20 ????10
????CaO ????1.5 ????8
????MgO ????1.5 ????2
????K 2O ????2 ????3
????Na 2O ????2 ????4
????Fe 2O 3 ????2
????TiO 2 ????1
????ZnO ????5
????ZrO 2 ????6
Yellow material ????2

Claims (3)

1. one kind has Nano self-cleaning overglaze sanitary ware, comprises ceramic body, ground-coat enamel and cover-coat enamel, it is characterized in that cover-coat enamel contains the Ag of median size less than 1 μ m 2O and ZnO composite nano germicide, the concrete Chemical Composition and the weight percentage thereof of cover-coat enamel are: SiO 250-70%, Al 2O 36-16%, CaO6-16%, MgO1-5%, K 2O1-5%, Na 2O1-5%, ZnO2-10%, Ag 2O0.1-3.0%.
2. according to the described sanitary ware of claim 1, it is characterized in that the Chemical Composition of cover-coat enamel and weight percentage thereof are: SiO 255-65%, Al 2O 38-12%, CaO6.5-9.5%, MgO1-2%, K 2O1.5-3.5%, Na 2O1.5-3.5%, ZnO2-8%, Ag 2O0.2-1.0%.
3. the manufacture method of the described sanitary ware of claim 1 is characterized in that preparation process may further comprise the steps:
(1) ground-coat enamel and cover-coat enamel material respectively water make slurries;
(2) ceramic spray glazing routinely, the ground-coat enamel slurries that step (1) is prepared spray equably on ready-made ceramic body, and its thickness is 0.2-0.7mm;
(3) the cover-coat enamel slurries of step (1) preparation are sprayed equably on the ground-coat enamel top layer of air dried step (2), its thickness is 0.1-0.5mm;
(4) ceramic blank drying that sprays ground-coat enamel and cover-coat enamel to moisture content less than after 0.5%, go into kiln and once be fired into transparent Nano self-cleaning overglaze sanitary ware, its firing temperature is 1150-1200 ℃, the time is 10-20 hour.
CNB021253110A 2002-07-24 2002-07-24 Sanitary ware with nano self-cleaning enamel and its making process Expired - Fee Related CN100357228C (en)

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Cited By (21)

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EP1881892A2 (en) * 2005-05-09 2008-01-30 American Standard International Inc. Antimicrobial glaze and porcelain enamel via double layer glaze with high zinc content
DE102007016500A1 (en) * 2007-03-26 2008-10-02 Eisenwerke Fried. Wilh. Düker GmbH & Co. KGaA Enamel coating for a body
CN101940221A (en) * 2010-08-30 2011-01-12 苏州邦安新材料科技有限公司 Novel sterilizing effervescent tablets and preparation process thereof
CN102190507A (en) * 2010-03-12 2011-09-21 广东蒙娜丽莎陶瓷有限公司 Glaze material, ceramic sheet and manufacturing method for ceramic sheet
CN101648824B (en) * 2008-08-15 2012-05-23 淄博博纳科技发展有限公司 Applique antibacterial ceramic cutter
CN102503571A (en) * 2011-10-20 2012-06-20 景德镇陶瓷学院 Ceramic glaze modifying additive and preparation method and application thereof
CN102515866A (en) * 2011-12-15 2012-06-27 广东顺祥陶瓷有限公司 Ceramic glaze with antibacterial capability and preparation method thereof
CN103102175A (en) * 2013-01-22 2013-05-15 广东尚高科技有限公司 Self-cleaning glaze and application thereof as well as ceramic sanitary ware
CN103387421A (en) * 2013-08-21 2013-11-13 景德镇市欧格陶瓷有限公司 Ceramic glaze with nanometer self-cleaning sterilization function and using method of ceramic glaze
CN103534100A (en) * 2011-04-21 2014-01-22 波利视觉股份有限公司 Antimicrobial enamelled visual communication panel.
CN104892032A (en) * 2015-05-15 2015-09-09 九牧厨卫股份有限公司 Lasting and easy cleaning surface glaze formula and method for preparing sanitary ware
WO2017138892A1 (en) 2016-02-08 2017-08-17 Kaleseramik Canakkale Kalebodur Seramik Sanayi Anonim Sirketi An inorganic antibacterial amorphous coating for ceramic surfaces
CN110123523A (en) * 2019-04-16 2019-08-16 温州大学 A kind of near-infrared stress type plasma diffusing W,Mo antiseptic dressing, the method and dressing combination that promote release
CN110128015A (en) * 2019-04-26 2019-08-16 苏州工业园区职业技术学院 A kind of enamel frit makeing method increasing glaze surface evenness
CN111423117A (en) * 2020-04-02 2020-07-17 厦门佳浴智能卫浴有限公司 Sanitary ware manufactured by adopting three-component glazing technology
CN111559869A (en) * 2020-07-15 2020-08-21 佛山瑭虹釉料科技有限公司 Antibacterial glaze material, antibacterial glazed tile and preparation method thereof
CN112028489A (en) * 2020-09-03 2020-12-04 赣州艺佳兴陶瓷有限公司 Ceramic glaze with antibacterial function and preparation method thereof
CN113087547A (en) * 2021-04-26 2021-07-09 吴国雄 Glaze firing process method for ceramic ware
CN113912296A (en) * 2021-11-26 2022-01-11 亚细亚建筑材料股份有限公司 Antibacterial and mildewproof ceramic glaze as well as preparation method and application thereof
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EP1881892A2 (en) * 2005-05-09 2008-01-30 American Standard International Inc. Antimicrobial glaze and porcelain enamel via double layer glaze with high zinc content
US10183896B2 (en) 2005-05-09 2019-01-22 Ideal Standard International Bvba Antimicrobial glaze and porcelain enamel via double layer glaze with high zinc content
US10427986B2 (en) 2005-05-09 2019-10-01 Ideal Standard International Bvba Antimicrobial glaze and porcelain enamel via double layer glaze with high zinc content
EP1881892A4 (en) * 2005-05-09 2012-05-30 American Standard Int Inc Antimicrobial glaze and porcelain enamel via double layer glaze with high zinc content
DE102007016500A1 (en) * 2007-03-26 2008-10-02 Eisenwerke Fried. Wilh. Düker GmbH & Co. KGaA Enamel coating for a body
CN101648824B (en) * 2008-08-15 2012-05-23 淄博博纳科技发展有限公司 Applique antibacterial ceramic cutter
CN102190507A (en) * 2010-03-12 2011-09-21 广东蒙娜丽莎陶瓷有限公司 Glaze material, ceramic sheet and manufacturing method for ceramic sheet
CN101940221A (en) * 2010-08-30 2011-01-12 苏州邦安新材料科技有限公司 Novel sterilizing effervescent tablets and preparation process thereof
CN101940221B (en) * 2010-08-30 2014-02-26 苏州泰利三佳纳米科技有限公司 Novel sterilizing effervescent tablets and preparation process thereof
CN103534100B (en) * 2011-04-21 2016-10-12 波利视觉股份有限公司 The visual communication panel of antimicrobial glazing
CN103534100A (en) * 2011-04-21 2014-01-22 波利视觉股份有限公司 Antimicrobial enamelled visual communication panel.
CN102503571A (en) * 2011-10-20 2012-06-20 景德镇陶瓷学院 Ceramic glaze modifying additive and preparation method and application thereof
CN102503571B (en) * 2011-10-20 2014-02-12 景德镇陶瓷学院 Ceramic glaze modifying additive and preparation method and application thereof
CN102515866A (en) * 2011-12-15 2012-06-27 广东顺祥陶瓷有限公司 Ceramic glaze with antibacterial capability and preparation method thereof
CN103102175A (en) * 2013-01-22 2013-05-15 广东尚高科技有限公司 Self-cleaning glaze and application thereof as well as ceramic sanitary ware
CN103387421A (en) * 2013-08-21 2013-11-13 景德镇市欧格陶瓷有限公司 Ceramic glaze with nanometer self-cleaning sterilization function and using method of ceramic glaze
CN104892032A (en) * 2015-05-15 2015-09-09 九牧厨卫股份有限公司 Lasting and easy cleaning surface glaze formula and method for preparing sanitary ware
WO2017138892A1 (en) 2016-02-08 2017-08-17 Kaleseramik Canakkale Kalebodur Seramik Sanayi Anonim Sirketi An inorganic antibacterial amorphous coating for ceramic surfaces
CN110123523A (en) * 2019-04-16 2019-08-16 温州大学 A kind of near-infrared stress type plasma diffusing W,Mo antiseptic dressing, the method and dressing combination that promote release
CN110128015A (en) * 2019-04-26 2019-08-16 苏州工业园区职业技术学院 A kind of enamel frit makeing method increasing glaze surface evenness
CN111423117A (en) * 2020-04-02 2020-07-17 厦门佳浴智能卫浴有限公司 Sanitary ware manufactured by adopting three-component glazing technology
CN111559869A (en) * 2020-07-15 2020-08-21 佛山瑭虹釉料科技有限公司 Antibacterial glaze material, antibacterial glazed tile and preparation method thereof
CN112028489A (en) * 2020-09-03 2020-12-04 赣州艺佳兴陶瓷有限公司 Ceramic glaze with antibacterial function and preparation method thereof
CN113087547A (en) * 2021-04-26 2021-07-09 吴国雄 Glaze firing process method for ceramic ware
CN113087547B (en) * 2021-04-26 2022-08-23 潮州市裕业陶瓷有限公司 Glaze firing process method for ceramic ware
CN113912296A (en) * 2021-11-26 2022-01-11 亚细亚建筑材料股份有限公司 Antibacterial and mildewproof ceramic glaze as well as preparation method and application thereof
CN115246709A (en) * 2022-08-01 2022-10-28 河北浩锐陶瓷制品有限公司 High-flatness ceramic tile and production process thereof
CN115504670A (en) * 2022-09-30 2022-12-23 景德镇陶瓷大学 Preparation method of high-glossiness sweet white glaze
CN115504670B (en) * 2022-09-30 2024-01-09 景德镇陶瓷大学 Preparation method of sweet white glaze with high glossiness

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