CN1319684A - Enamel products - Google Patents
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- CN1319684A CN1319684A CN 00134890 CN00134890A CN1319684A CN 1319684 A CN1319684 A CN 1319684A CN 00134890 CN00134890 CN 00134890 CN 00134890 A CN00134890 A CN 00134890A CN 1319684 A CN1319684 A CN 1319684A
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Abstract
The invention provides an enameled product such as a bathtub, a sink and a wash bowl having a function capable of easily removing stains over a long period with high reproducibility by allowing the surface roughness of the surface of a glaze layer as the upper most layer to be easy to be controlled to <0.6 &mu m regardless of the variation in the production. In this enameled product, on the surface of a metallic base material, a colored emulsifiable first glaze layer has been formed, and moreover, on the surface, a transparent second glaze layer has been formed, the thickness of the second glaze layer is controlled to >=0.5 mm.
Description
The present invention relates to a kind of enamelware, this enamelware can be kept the performance of removing dirt easily for a long time enduringly, is a kind of formation bathroom floor, wall, bathrooms such as top ceiling building materials, be to be used for bath, the revetment of bath, washing basin, the washing basin backboard, tank, kitchen wall dunnage, the enamelware of backstairs etc.
In the past, bath, tank, the casting enamelware of washing basin etc. generally were the metallic substrate surface coating one deck glaze layers at casting.As glaze, use the silica (quartz) of natural matter, borax, the sintering glaze of fusion such as SODA ASH LIGHT 99.2 in addition, also adds weisspiessglanz, zircon and pigment as opacifying agent.
But the method before above-mentioned is on the glaze layer surface, because the particle exposing surface of the particle of weisspiessglanz or zircon and pigment forms protuberance.Therefore, the surfaceness of measuring with contact pin type surface roughness measurement device (JIS-B0651) (Ra) is more than the 0.06 μ m, and dirt perhaps is difficult to come off easily in the pottery surface attachment.
Keeping the sanitation and hygiene on enamelware surface and keep long-lasting attractive in appearance admirably, is the necessary characteristic as the general widely used enamelware of daily necessities.
Since ancient times, as in general family, keeping the sanitation and hygiene on enamelware surface and keep long-lasting method attractive in appearance admirably, can take to use tensio-active agent, acid, Xian Di agent such as alkali are carried out dashing and sweep and scrub energetically to the enamelware surface, so that remove the method for crude removal.
But this method is looked the degree that dirt adheres to, and dashes to sweep and scrub to require to pay work.Particularly for the elderly, each required work is all too serious.
Simultaneously, in recent years, scolded contaminate environment, wished to reduce the consumption and the frequency of tensio-active agent owing to contain the draining of tensio-active agent.
Do not use tensio-active agent, and do not adopt energetically the method for sweeping and scrubbing of dashing, as the enamelware surface is kept hygienically clean, and keep method attractive in appearance admirably, two kinds of methods are roughly arranged.
One of method is the method that forms the enamelware surface be difficult to adhere to dirt with chemical process.Prior art has proposed (1) with the enamelware surface roughening, apply in its surface then fluoro-resin method and, (2) contain the method for the silicone resin of fluoroalkyl in the surface applied of enamelware, be exposed to the surface, make dirt be difficult to adhere to owing to can reduce the fluorin radical of surface energy.
This method since the thermotolerance of compound that contains fluorin radical below 400 ℃, the enamelware sintering can not apply above-mentioned resin in the past, therefore to apply later at the enamelware sintering, and for to make hardening of resin that the operation of heating must be arranged, increased operation like this, improved manufacturing expense, can only say on principle it is a kind of good method.
Two of method is the methods that form the enamelware surface be difficult to adhere to dirt with physical method, promptly makes smooth surface as far as possible, prevents that dirt is attached to the surface of enamelware securely, washes method except that crude removal simply with flowing water.
This method is the method that proposes since ancient times, but in the former enamelware, for example observes the water line position of bath of life-time service and the dirt of baffle plate position accumulation, can fully remove crude removal hardly.
In order to address the above problem, the applicant has proposed coating first glaze layer and second glaze layer on metallic substance, and second glaze layer uses the method (the special flat 11-115474 of hope) of the sintering glaze that does not contain opacifying agent and pigment.
The applicant is the result of the above-mentioned application of research further, has found following phenomenon:
(1) be regardless of we in the difference of making, the glaze layer surfaceness that all exists top layer easily is lower than the condition of 0.06 μ m.
(2) be regardless of the difference of we on making, all exist crack that is difficult for the generation bad order and the condition of peeling off.
(3) be regardless of the difference of we on making, all exist the condition of easy control tone.
First working of an invention scheme provides a kind of enamelware, it is characterized in that forming painted milkiness first glaze layer that contains opacifying agent and tinting material on the surface of metal base, form the transparency second glaze layer that does not contain opacifying agent and tinting material then thereon, the thickness of second glaze layer is more than 0.5mm.
Because the thickness of second glaze layer more than 0.5mm, is regardless of the difference of we on making, the surfaceness on the second glaze layer surface makes easily and is lower than 0.06 μ m.
The surface of also considering second glaze layer is not subject to the weisspiessglanz particle and the zircon particle that contain in first glaze layer, the influence of pigment particles.
In the preferred embodiment of first invention, the thickness of first glaze layer is more than the 0.3mm.
Owing to more than the thickness 03mm of first glaze layer, be regardless of the difference of we on making, be difficult for taking place tonal variation for the original tone of first glaze layer.
In the preferred embodiment of first invention, the thickness of the thickness of first glaze layer and second glaze layer total is lower than 2.5mm.
Be lower than 2.5mm because the thickness of the thickness of first glaze layer and second glaze layer adds up to, be regardless of the difference of we on making, be difficult for taking place the crack and peel off etc.
In another embodiment of first invention, a kind of enamelware will be provided, it is characterized in that in metallic substrate surface, formation contains milkiness first glaze layer of opacifying agent, form second glaze layer that contains tinting material and do not contain the painted transparency of opacifying agent then thereon, further form the transparency the 3rd glaze layer that does not contain opacifying agent and tinting material thereon, the thickness of above-mentioned second, third glaze layer is aggregated in more than the 0.5mm.
Because the thickness and the 3rd glaze layer thickness of second glaze layer are aggregated in more than the 0.5mm, be regardless of the difference of we on making, the surfaceness on the 3rd glaze layer surface is lower than 0.06 μ m easily.
The surface of also considering the 3rd glaze layer is not subject to the weisspiessglanz particle that contains in first glaze layer and the influence of zircon particle.
In the preferred embodiment of first invention, the thickness of above-mentioned the 3rd glaze layer is more than the 0.15mm.
Because more than the thickness 0.15mm of the 3rd glaze layer, be regardless of the difference of we on making, the surfaceness on the 3rd glaze layer surface is lower than 0.06 μ m easily.
This is because the surface of the 3rd glaze layer, is not subject to the influence of the pigment particles that contains in second glaze layer.
In the preferred embodiment of the invention, the thickness of first glaze layer is more than the 0.3mm.
Because the thickness of first glaze layer is more than the 0.3mm, be regardless of the difference of we on making, be difficult for the tonal variation of generation for the original tone of first glaze layer.
In the preferred embodiment of first invention, the thickness of the thickness of first glaze layer and second glaze layer and the thickness of the 3rd glaze layer total are lower than 2.5mm.
Be lower than 2.5mm because the thickness of the thickness of first glaze layer and second glaze layer and the thickness of the 3rd glaze layer add up to, be regardless of the difference of we on making, be difficult for taking place the crack and peel off etc.
The inventor develops the enamelware that surface roughness Ra is lower than 0.06 μ m for the first time for the result of enamelware manufacturing process further investigation.
The main points of making are as the raw material that forms the most surperficial glaze of enamelware, only use vitrified in advance glaze raw material (the glaze raw material of preferred glassization is not blocky, but miniaturization).
Second invention provides a kind of enamelware, it is characterized in that forming in metallic substrate surface the enamelware of glaze layer, and the phase rugosity Ra on above-mentioned glaze layer surface is lower than 0.06 μ m, below the preferred 0.05 μ m, more preferably below the 0.03 μ m.
Because the enamelware surface has smoothness never, dirt is difficult for adhering to securely, consequently, even adhere to, can float owing to contacting with water, floats the dirt that comes and can wash out with current.
The phase rugosity Ra on enamelware glaze layer surface in the past is more than 0.06 μ m, and there is big concavo-convex existence on the surface, and glaze layer of the present invention surface is very smooth, only exists very little concavo-convex.
Suppose two surface attachment identical type this moment, the dirt of identical size, and the adhesion strength between dirt and the glaze layer surface relatively, the former enamelware adhere firmly that contact surface is big, and the level and smooth surperficial contact surface of the present invention is little, a little less than therefore adhering to.
Secondly, when the whole waters of dirt surround, with the irrelevant onesize dirt of condition of surface, produce onesize buoyancy, as mentioned above for the strong former enamelware of adhere firmly, dirt is difficult for come-up, enamelware for smooth-flat-surface of the present invention, dirt floats easily, in case come-up can be washed out with flowing water, recovers original clean Surface.
In second invention embodiment preferred, in above-mentioned glaze layer, do not contain emboliform material.
The inventor confirms with electron microscope, and former enamelware forms surface roughness Ra big concavo-convex major cause more than 0.06 μ m, is because the influence of opacifying agent particle such as weisspiessglanz particle and zircon particle or pigment particles.
If therefore glaze layer does not contain the material of above-mentioned particle state, make the enamelware surface have never smoothness easily, can provide reproducibility better, the surfaceness of above-mentioned laminar surface is lower than 0.06 μ m, below the preferred 0.05 μ m, the more preferably following enamelware of 0.03 μ m.
The invention provides a kind of enamelware, it is characterized in that forming first glaze layer of tint permanence in metallic substrate surface, form the enamelware of second glaze layer that does not contain particle-like substance then on the surface of first glaze layer, the surface of above-mentioned second glaze layer is measured with contact pin type surface roughness measurement device (JIS-B0651), its Ra is lower than 0.06 μ m, below the preferred 0.05 μ m, more preferably below the 0.03 μ m.
Because the enamelware surface has smoothness never, dirt is difficult for adhering to securely, even adhere to, can float owing to contacting with water, floats the dirt that comes and can wash out with current.
And, can give Art Pattem Design according to particle shape pigment or opacifying agent owing to can design the artistic pattern of tint permanence in lower floor.
In the preferred embodiment of second invention, second glaze layer is transparent.
Therefore utilize the production art design of first glaze layer, can easily control tone.
In the preferred embodiment of second invention, it is the enamelware that forms glaze layer on the surface of metal base, above-mentioned is to form contact angle with water to be lower than 30 ° by medicine layer or above-mentioned transparent glaze laminar surface, preferred below 25 °, more preferably the hydrophilic surface below 20 °.
The enamelware surface in the past and the contact angle height of water, because the interface capillary phenomenon on dirt and glaze layer surface, water is not easy to immerse.On the other hand, the enamelware on possess hydrophilic property surface, owing to capillary phenomenon, the water capacity easily immerses on same interface, and dirt can float.And, form moisture film at hydrophilic surface in water mobile occasion, and can prevent from water, to float the dirt that comes and be attached to the surface again, have easy mobile effect.
In addition, the inventor finds that according to the above-mentioned enamelware of analyzing life-time service the reason of long-term smoothness reduction is relevant with the weisspiessglanz concentration in the glaze.In weisspiessglanz, be used as the control coloring effects such as iron that the impurity in the glaze contains, in the enamel glaze, generally must contain a kind of such composition, in case but the concentration of weisspiessglanz raises, the part that weisspiessglanz concentration is high in the glaze produces striped, because this part is poor with part solidity to corrosion on every side, life-time service forms concavo-convex, and smoothness is reduced.
Therefore, by the concentration of controlled oxidation antimony, even can develop life-time service the time smoothness reduce little, non-staining glaze.
The 3rd invention provides a kind of enamelware, it is characterized in that on metal base forming the enamelware of surperficial glaze layer, and the concentration of the weisspiessglanz that contains in the above-mentioned surperficial glaze layer is lower than 2wt%, below the preferred 1.5wt%, and the more preferably following enamelware of 1wt%.Or on metal base, form the tint permanence glaze layer, and further it goes up the enamelware that forms surperficial glaze layer again, and the concentration of the weisspiessglanz that contains in the above-mentioned surperficial glaze layer is lower than 2wt%, below the preferred 1.5wt%, the more preferably enamelware below the 1wt%.
The solidity to corrosion distinct portions so seldom occurs, can suppress the increase of surfaceness during life-time service.Therefore enamelware just is difficult for adhering to dirt from the beginning of using, and removes easily, can keep cleaning for a long time enduringly.
Enamelware in the past, the weisspiessglanz concentration in the surperficial glaze layer is about 1-2wt%, so during life-time service, part that weisspiessglanz concentration is high and the solidity to corrosion of peripheral part are poor, form concavo-convex, the surface smoothing reduction, dirt adheres to easily, is not easy to remove.And very little because of the high part of surperficial glaze layer weisspiessglanz concentration of the present invention, the surface smoothing reduction is very little during life-time service.
In the preferred embodiment of the 3rd invention, provide to it is characterized by in the above-mentioned surperficial glaze layer weisspiessglanz concentration more than 0.001wt%, more than the preferred 0.01wt%, the more preferably above enamelware of 0.1wt%.
Because add the weisspiessglanz of trace in surperficial glaze layer, glaze layer is not painted, become transparent layer fully, the control tone becomes simple.
Be oxidized to 5 valencys by 3 valencys during the antimony sintering, the iron that contains as impurity in the surperficial glaze layer is reduced, and can control painted effectively.
Because the enamelware surface has smoothness never, dirt is difficult for adhering to securely, even its result adheres to, owing to contact and can float with water, floating the dirt that comes can wash away with flowing water.
In addition, owing to can design the structure of the artistic pattern layer of tint permanence, can give Art Pattem Design according to particle shape pigment or opacifying agent in lower floor.
In the preferred version of the 3rd invention, second glaze layer is transparent.Therefore can utilize the Art Pattem Design of first glaze layer, and control tone easily.
First working of an invention scheme at first is described.About the pigment of first invention, cobalt compound is for example arranged, iron cpd etc.; As opacifying agent, weisspiessglanz is for example arranged, zircon, titanium oxide, stannic oxide etc.
As the sintering glaze, be glaze raw material that the mixture from above-mentioned natural mineral particle etc. is obtained in high-temperature fusion, promptly so-called vitrified glaze.
In first invention, at first prepare not contain the transparent glaze of opacifying agent and tinting material,, vitrified sintering glaze is mixed in ball mill etc. for this reason with above-mentioned glaze raw material high-temperature fusion, also can pulverize as required, also can buy commercially available transparent glaze.
Secondly prepare to contain tinting material, do not contain the painted transparent glaze of opacifying agent, painted transparent glaze is with the mixing in ball mill etc. of transparent glaze and pigment, pulverizes as required and can obtain.
Prepare to contain the painted milkiness glaze of opacifying agent and tinting material then.Painted milkiness glaze is that transparent glaze and pigment and opacifying agent are mixed in ball mill etc., pulverizes as required and can obtain.
As metal base, for example, preferably can use is at cast iron, and aluminium, stainless steel etc. are gone up the base material of coating ground-coat enamel medicine, or utilizes the base material at the surface coverage oxide film of acid treatment or sintering processes.
In addition, coating ground-coat enamel medicine on metal base behind 800-1100 ℃ of sintering, is used dry enamelling colored coating opaque glaze under heated condition.Join the interior calcining of kiln after 1-2 minute, down with dry enamelling colored coating transparency glaze, join again in kiln and calcined 1-2 minute in heated condition.Further apply transparent glaze, calcined 0.5-1 minute, form the surface smoothing functional layer with dry enamelling.
Table 1
| The glaze base material | Weight wt% |
| ????SiO 2 | ????45-65 |
| ????Al 2O 3 | ????0.01-1??? |
| ????Fe 2O 3 | ????0.01-0.3 |
| ????B 2O 3 | ????2-10 |
| ????CaO | ????0.4-3 |
| ????ZnO | ????0.5-3 |
| ????TiO 2 | ????3-10 |
| ????Na 2O | ????3-15 |
| ????ZrO 2 | ????1-10 |
| ????BaO | ????1-5 |
| ????Sb 2O 3 | ????1-2 |
| ????Li 2O | ????2-7 |
| ????F 2 | ????1-4 |
Sintering glaze 2kg and stone ball 4kg that table 1 is formed join in the pottery pot of 6 liters of volumes, pulverize in ball mill, make it all by 150 purposes sieve, and the powder that obtains like this is as glaze A (transparent glaze approximately).
Be different from above-mentioned, sintering glaze 2kg and the opacifying agent (titanium oxide) that table 1 is formed and pigment is counted g and stone ball 4kg joins in the pottery pot of 6 liters of volumes, pulverize in ball mill, make it all by 150 purposes sieve, the powder that obtains like this is as glaze B (tint permanence milkiness glaze).
Next makes the plate-shape metal test film of 100 * 100mm and the bath of casting, coating ground-coat enamel medicine sintering, to be coated on the tabular test film with dry enamelling as the above-mentioned glaze B that obtains (tint permanence milkiness glaze), more thereon with dry enamelling coating glaze A (transparent glaze).At this moment, can regulate the glaze B (tint permanence breast worm) that changes on the tabular test film, the thickness of glaze A (transparent glaze).In 800-1100 ℃ of sintering, obtain test portion.
The glaze surfaceness (Ra) of the tabular test film that mensuration obtains is confirmed glaze color and luster and the apparent shortcoming of manufacturing.
Surfaceness is measured the roughness (Ra) on medullary ray surface with contact pin type surface roughness measurement device (JIS-B0651).
Visual Confirmation glaze color and luster and the apparent shortcoming of manufacturing.
Respectively the results are shown in table 2, when the thickness of glaze A (transparent glaze) reaches 0.1mm, because its thickness low LCL, be difficult to the concavo-convex covering fully that will cause owing to the opacifying agent (weisspiessglanz) that contains among the glaze B (tint permanence milkiness glaze) and pigment particles, making it does not have influence, and surfaceness (Ra) is 0.06 μ m.
In addition, when the thickness of glaze A (transparent glaze) and glaze B (tint permanence milkiness glaze) added up to 2.6mm, the crack took place in glaze layer, and a part begins to peel off.
In addition, when the thickness of glaze B (tint permanence milkiness glaze) reached 0.2mm, owing to seen through the color of metal base, transparency descended slightly, and the different tendency of some tones is arranged.When but surfaceness (Ra) is lower than 0.06 μ m, still has the performance of removing crude removal easily.
Further bath is carried out same affirmation, carry out confirming with the same situation of test film.
Table 2
| Thickness (mm) | The outward appearance shortcoming | Ra(μm) | ||
| The first layer | The second layer | |||
| ?1 | ????0.6 | ????0.6 | ?0.03 | |
| ?2 | ????0.2 | ????0.5 | Some tonal variation | ?0.04 |
| ?3 | ????0.6 | ????0.1 | The surface takes place concavo-convex | ?0.06 |
| ?4 | ????1.6 | ????1.0 | The crack, peel off | ?- |
Sintering glaze 2kg and stone ball 4kg that table 1 is formed join in the pottery pot of 6 liters of volumes, pulverize in ball mill, make it all by 150 purposes sieve, and the powder that obtains like this is as glaze A (transparent glaze).
Be different from above-mentionedly, the sintering glaze 2kg that table 1 is formed and pigment is counted g and stone ball 4kg joins in the pottery pot of 6 liters of volumes pulverizes in ball mill, and it is all sieved by 150 purposes, and the powder that obtains like this is as glaze C (the transparent glaze of tint permanence).
Be different from above-mentioned, sintering glaze 2kg and the opacifying agent (weisspiessglanz) that table 1 is formed and pigment is counted g and stone ball 4kg joins in the pottery pot of 6 liters of volumes, pulverize in ball mill, make it all by 150 purposes sieve, the powder that obtains like this is as glaze B (tint permanence milkiness glaze).
Next makes the plate-shape metal test film of 100 * 100mm and the bath of casting, coating ground-coat enamel medicine sintering, to be coated on the tabular test film with dry enamelling as the above-mentioned glaze B that obtains (tint permanence milkiness glaze), again thereon with dry enamelling coating glaze C (the transparent glaze of tint permanence), further thereon with dry enamelling coating glaze A (transparent glaze).Can regulate the glaze B (tint permanence milkiness glaze) that changes on the tabular test film, the thickness of glaze C (the transparent glaze of tint permanence), glaze A (transparent glaze) this moment.In 800-1100 ℃ of sintering, obtain test portion.
The glaze surfaceness (Ra) of the tabular test film that mensuration obtains is confirmed glaze color and luster and the apparent shortcoming of manufacturing.
Surfaceness is measured the roughness (Ra) on medullary ray surface with contact pin type surface roughness measurement device (JIS-B0651).
Visual Confirmation glaze color and luster and the apparent shortcoming of manufacturing.
Respectively the results are shown in table 3, when the thickness of glaze A (transparent glaze) was 0.05mm, because thickness low LCL, being difficult to will be owing to concavo-convexly covering that the pigment particles that contains among the glaze C (the transparent glaze of tint permanence) causes fully, making it does not have influence, and surfaceness (Ra) is 0.06 μ m.
In addition, when the thickness of the thickness of glaze A (transparent glaze) and glaze C (the transparent glaze of tint permanence) adds up to 0.2mm, because thickness low LCL, being difficult to will be owing to concavo-convexly covering that opacifying agent (weisspiessglanz) particle that contains among the glaze B (tint permanence milkiness glaze) causes fully, making it does not have influence, and surfaceness (Ra) is 0.06 μ m.
In addition, when the thickness of the thickness of the thickness of glaze A (transparent glaze) and glaze C (the transparent glaze of tint permanence) and glaze B (tint permanence milkiness glaze) added up to 2.6mm, the crack took place in glaze layer, and a part begins to peel off.
In addition, when the thickness of glaze B (tint permanence milkiness glaze) was 0.2mm, owing to seen through the color of metal base, transparency descended slightly, and the different tendency of some tones is arranged.When but surfaceness (Ra) is lower than 0.06 μ m, still has the performance of removing crude removal easily.
Further bath is carried out same affirmation, carry out having the affirmation of kindred circumstances with test film.
Table 3
| Thickness (mm) | The outward appearance shortcoming | Ra(μm) | |||
| The first layer | The second layer | The 3rd layer | |||
| ?1 | ?0.6 | 0.5 | 0.2 | ????0.03 | |
| ?2 | ?0.2 | 0.5 | 0.2 | Some tonal variation | ????0.04 |
| ?3 | ?0.6 | 0.6 | 0.05 | The surface takes place concavo-convex | ????0.06 |
| ?4 | ?0.6 | 0.05 | 0.15 | The surface takes place concavo-convex | ????0.06 |
| ?5 | ?1.0 | 1.0 | 0.6 | The crack, peel off | ????- |
Second working of an invention scheme below is described.
The enamelware of second invention is to form glaze layer on metal base, and the surface roughness Ra on the surface of glaze layer is lower than 0.06 μ m, below the preferred 0.05 μ m, more preferably below the 0.03 μ m.
Here, surface roughness Ra (JIS-B0601) is measured and can be obtained according to contact pin type surface roughness measurement device (JIS-B0651).
Contact angle with surface water is lower than 30 ° in addition, and is preferred below 25 °, more preferably below 20 °.
Here and the contact angle of water according to the method for dripping, can measure with the contact angle determination device and obtain.
Metal base be fit to utilize for example at iron (steel plate, castings) base material, stainless steel substrate, aluminium base, copper base material etc. are gone up the base material of coating ground-coat enamel medicine, or acid treatment or by sintering processes etc. at the base material of surface coverage oxide film etc.
Second enamelware that invention may utilize though there is not the restriction of the following stated, can be for example to constitute bathroom floor, wall, the bathroom building materials of top ceiling, bath, the revetment of bath, washing basin, the washing basin backboard, tank, kitchen wall dunnage, backstairs etc.
For example, the metallic soap dirt that bathroom floor, shower wall are adhered to, or the incrustation scale dirt of the revetment board of bath, the oily pollutant of bath water line portion, the mucus dirt of bath bottom can be removed simply with the flowing water of shower etc.In addition, the backboard of the backboard in kitchen or washing basin can water be examined gently and is wiped crude removal off.And, can be with water wipings such as tank or washing basins, or in the pond behind the ponding, ponding such as is removed at simple method remove.
In addition, use in bath bottom the time of the present invention, preferably carry out the big concavo-convex processing of embossing etc. on the sheet metal before glazing, so that anti-sliding stop.
Make a method of the enamelware of second invention, comprise the step of preparing fine vitrifying sintering shape glaze raw material, above-mentioned glaze raw material is coated on the step and the sintering step of metal base.
Here, as fine vitrifying sintering shape glaze raw material, can be with from silica sand, borax, SODA ASH LIGHT 99.2, pigment, the glaze raw mix of opacifying agent etc. obtains in high-temperature fusion more than 1100 ℃.
In addition,, can utilize spraying and applying, dip coating, spin coated, damp process or heating dry type glaze application methods such as roller coating, the general method of the drying process of dry-fine method etc. as the method that the glaze raw material is coated on the metal base.
Sintering temperature can be different according to glaze composition or metal base, is about 300-1100 ℃.
Make other method of the enamelware of second invention, comprise that preparation does not contain the transparent vitrifying sintering shape glaze raw material of pigment and opacifying agent, and under sintering temperature, can be fused to the step of the pigment opacifying agent in the glass admittedly, the mixture of above-mentioned sintering shape glaze raw material and pigment opacifying agent is coated on step and sintering step on the metal base.
Here, as fine vitrifying sintering shape glaze raw material, can be with from silica sand, borax, the glaze raw mix of SODA ASH LIGHT 99.2 etc. obtains in high-temperature fusion more than 1100 ℃.
In addition,, can utilize spraying and applying, dip coating, spin coated, damp process or heating dry type glaze application methods such as roller coating, the general method of the drying process of dry-fine method etc. as the method that the glaze raw material is coated on the metal base.
Sintering temperature can be different according to glaze composition or metal base, is about 300-1100 ℃.
Make other method of the enamelware of second invention, comprise that preparation contains the step of the tint permanence glaze raw material of pigment and opacifying agent, above-mentioned tint permanence glaze raw material is coated on the step that forms the tint permanence glaze layer on the metal base, prepare the step of fine vitrifying sintering shape glaze raw material, above-mentioned vitrifying sintering shape glaze raw material is coated on step and sintering step on the painted glaze layer.
Here, as fine vitrifying sintering shape glaze raw material, can be with from silica sand, borax, the glaze raw mix of SODA ASH LIGHT 99.2 etc. obtains in high-temperature fusion more than 1100 ℃.
In addition,, can utilize spraying and applying, dip coating, spin coated, damp process or heating dry type glaze application methods such as roller coating, the general method of the drying process of dry-fine method etc. as the method that the glaze raw material is coated on the metal base.
Sintering temperature can be different according to glaze composition and metal base, is about 300-1100 ℃.
Also can in glaze layer, add glaze additive in addition, make it have other additional performance.
For example add silver, copper, the antibacterial metal of zinc or its compound, Solid solution etc., or titanium oxide, zinc oxide, stannic oxide, ferric oxide, tungstic oxide, strontium titanate, photocatalysts such as bismuthous oxide bismuth trioxide can make it have antibacterial effect.
In addition, add above-mentioned photocatalyst and can improve wetting ability.The comparative example 1 of second invention
With SiO
2-B
2O
3-Na
2O be the glaze raw material formed of the above-mentioned table 1 of main component in electric furnace in 1100-1400 ℃ of fusion, quenching in water obtains the vitrifying sinter.With vitrifying sinter 2kg and opacifying agent (weisspiessglanz) and pigment is counted g and stone ball 4kg joins in the pottery pot of 6 liters of volumes, in ball mill, pulverize, make it all by 150 purposes sieve, the powder that obtains like this is as glaze.The glaze powder that obtains like this is as glaze A.
Secondly, on the tabular metallographictest sheet of the cast iron of 100 * 100mm,,, with dry enamelling coating glaze A, in 800-1100 ℃ of sintering, obtain the enamel test portion again in heated condition in 800-1100 ℃ of sintering with wet type glazing method coating ground-coat enamel medicine.
The enamel test portion that obtains is carried out the mensuration of surfaceness and the mensuration of water contact angle, carry out oiliness trace washing test.
The surfaceness of enamel test portion glaze layer is measured medullary ray surface roughness Ra ((JIS-B0601) with contact pin type surface roughness measurement device (JIS-B0651).It is Ra=0.06 μ m as a result.In addition, with atomic force microscope (AFM; Degital Instruments makes, Nano Scope III) measure the surfaceness of 100 * 100 mu m ranges, Ra=7.5nm.
The enlarged view such as the Fig. 3 (a) on the surface that obtains with the surface roughness measurement device are with scanning electronic microscope (SEM; The Hitachi, the surperficial secondary electron image that S-800) obtains such as Fig. 4 (a); With the observable surperficial enlarged view of atomic force microscope (AFM) such as Fig. 5 (a).
(manufacturing of consonance interface science CA-X150), drips to specimen surface with water droplet and measured after last 30 second the contact angle of enamel test portion glaze layer and water from microsyringe, the result is 31 ° with the contact angle determination device.
Tack and detergency about dirt, carrying out formula with the oiliness trace tests, test method is the oiliness trace that forms black in the φ 10mm scope of test portion surface, (magic ink 700#), about 1 minute of drying at room temperature, whether the 3ml water that drips is then observed trace and is floated, and whether trace is rinsed and flows down when test portion tilted.Its result, trace does not float on the surface, even the inclination test portion, the still residual trace in surface.Second inventive embodiment 1
Identical with comparative example 1, in 1100-1400 ℃ of fusion, quenching in water obtains the vitrifying sinter to the glaze raw material that table 1 is formed in electric furnace.This vitrifying sinter 2kg and stone ball 4kg are joined in the pottery pot of 6 liters of volumes, pulverize in ball mill, make it all by 150 purposes sieve, the powder that obtains like this is as glaze, and the glaze powder that obtains like this is as glaze B.
Secondly on the tabular metallographictest sheet of the cast iron of 100 * 100mm, apply the ground-coat enamel medicine with wet type glazing method, in 800-1100 ℃ of sintering, apply glaze A in heated condition with dry enamelling, again in 800-1100 ℃ of sintering, apply glaze B in heated condition with dry enamelling then, in 800-1100 ℃ of sintering, obtain the enamel test portion again.
The test portion that obtains is carried out the evaluation same with comparative example 1, the result of the mensuration of surfaceness, contact pin type: Ra=0.03 μ m, AFM:Ra=2.9nm.
The enlarged view such as the Fig. 3 (b) on the surface that obtains with the surface roughness measurement device, surperficial secondary electron image such as Fig. 4 (a) of obtaining with scanning electronic microscope (SEM); With the observable surperficial enlarged view of atomic force microscope (AFM) such as Fig. 5 (b).
With the contact angle determination result of water be 16 °.
About the tack and the detergency of trace, water droplet is floatation surface on the 30 seconds traces in back down, and trace and water flowed down together when test portion was tilted, and the surface does not have trace fully.The 3rd working of an invention scheme below is described.
In the embodiment of the enamelware of the 3rd invention, be coating ground-coat enamel medicine on metal base, form the tint permanence glaze layer more thereon, form the surperficial glaze layer of the transparency then on its surface.Here, in surperficial glaze layer, weisspiessglanz is lower than 2wt%, below the preferred 1.5wt%, more preferably below the 1wt%.Further in second glaze layer, weisspiessglanz is more than the 0.001wt%, more than the preferred 0.01wt%, more preferably more than the 0.1wt%.
The making method of above-mentioned enamelware, for example comprise that the tint permanence glaze raw material that will contain pigment or opacifying agent is coated on the step that sintering behind the metal base forms the tint permanence glaze layer, is coated on agglomerating step on the painted glaze layer with fine vitrifying sintering shape glaze raw material.
Here, as fine vitrifying sintering shape glaze raw material, can be with from silica sand, borax, the glaze raw mix of SODA ASH LIGHT 99.2 etc. obtains in high-temperature fusion more than 1100 ℃.
In addition,, can utilize spraying and applying, dip coating, spin coated, damp process and heating dry type glaze application methods such as roller coating, the general method of the drying process of dry-fine method etc. as the application process of glaze raw material.
Sintering temperature can be different according to glaze composition or metal base, about 300-1100 ℃ of sintering.
Other embodiment of the enamelware of the 3rd invention is a coating ground-coat enamel medicine on metal base, forms the surperficial glaze layer of tint permanence more thereon.Here, in surperficial glaze layer, weisspiessglanz is lower than 2wt%, below the preferred 1.5wt%, more preferably below the 1wt%.Further in above-mentioned surperficial glaze layer, weisspiessglanz is more than the 0.001wt%, more than the preferred 0.01wt%, more preferably more than the 0.1wt%.
The making method of above-mentioned enamelware for example comprises and will not contain the transparent vitrifying sintering shape glaze raw material of pigment or opacifying agent and can be fused to step and the sintering step that pigment opacifying agent mixture in the glass is coated on metal base admittedly under sintering temperature.
Here, as fine vitrifying sintering shape glaze raw material, can be with from silica sand, borax, the glaze raw mix of SODA ASH LIGHT 99.2 etc. obtains in high-temperature fusion more than 1100 ℃.
In addition,, can utilize spraying and applying, dip coating, spin coated, damp process and heating dry type glaze application methods such as roller coating, the general method of the drying process of dry-fine method etc. as the application process of glaze raw material.
Sintering temperature can be different according to glaze composition or metal base, about 300-1100 ℃ of sintering.
Metal base be fit to utilize, for example at iron (steel plate, castings) base material, and stainless steel substrate, aluminium base, copper base material etc. or apply the base material of ground-coat enamel medicine thereon, or by the base material at the surface coverage oxide film such as acid treatment or sintering processes.
The 3rd enamelware that invention may utilize though there is not the restriction of the following stated, can be for example to constitute bathroom floor, wall, the bathroom building materials of courtyard, bath, the revetment of bath, washing basin, the washing basin backboard, tank, kitchen wall dunnage, backstairs etc.
For example, bathroom floor, the metallic soap dirt that shower wall is adhered to, dirt with the revetment board of bath, the greasy dirt of bath water line portion, the mucus dirt of bath bottom can be removed simply with the flowing water of shower etc., the backboard in kitchen in addition, the backboard of backstairs and washing basin can water be examined gently and are wiped crude removal off.And can be with water wipings such as tank and washing basins, in the pond behind the ponding, ponding such as is removed at simple method remove.
Use in bath bottom the time of the present invention, preferably carry out the big concavo-convex processing of embossing etc. on the sheet metal before glazing, so that anti-sliding stop.The comparative example 1 of the 3rd invention
In 1100-1400 ℃ of fusion, quenching in water obtains the vitrifying sinter to the glaze raw material that table 1 is formed in electric furnace.With vitrifying sinter 2kg and opacifying agent (weisspiessglanz) and pigment is counted g and stone ball 4kg joins in the pottery pot of 6 liters of volumes, in ball mill, pulverize, make it all by 150 purposes sieve, the powder that obtains like this is as glaze.The glaze powder that obtains like this is as glaze A.
Table 4
| The glaze base material | Weight % |
| ????SiO 2 | ????45-65 |
| ????Al 2O 3 | ????0.01-1 |
| ????Fe 2O 3 | ????0.01-0.3 |
| ????B 2O 3 | ????2-10 |
| ????CaO | ????0.4-3 |
| ????ZnO | ????0.5-3 |
| ????TiO 2 | ????3-10 |
| ????Na 2O | ????3-15 |
| ????ZrO 2 | ????1-10 |
| ????BaO | ????1-5 |
| ????Li 2O | ????2-7 |
| ????F 2 | ????1-4 |
Add weisspiessglanz 2wt% in the glaze raw material that table 4 is formed, in 1100-1400 ℃ of fusion, quenching in water obtains the vitrifying sinter in electric furnace.Vitrifying sinter 2kg and stone ball 4kg are joined in the pottery pot of 6 liters of volumes, pulverize in ball mill, make it all by 150 purposes sieve, the powder that obtains like this is as glaze, and the glaze powder that obtains like this is as glaze B.
Secondly on the tabular metallographictest sheet of the cast iron of 100 * 100mm, apply the ground-coat enamel medicine with wet type glazing method, in 800-1100 ℃ of sintering, apply glaze A in heated condition with dry enamelling, again in 800-1100 ℃ of sintering, apply glaze B in heated condition with dry enamelling then, in 800-1100 ℃ of sintering, obtain the enamel test portion again.
The enamel test portion that obtains is boiled in the NaOH of the 5wt% aqueous solution, flooded 3 hours, obtain the accelerated test test portion.
Enamel test portion that obtains and accelerated test test portion atomic force microscope (AFM; Degital Instruments makes, Nano Scope III) be determined at the surperficial phase rugosity of 100 * 100 scopes, enamel test portion: Ra=2.9nm, accelerated test test portion: Ra=27nm.The observable surperficial enlarged view of each atomic force microscope (AFM) such as Fig. 6 (a1) and Fig. 6 (a2); Electron probe micro-analysis device (EPMA; NEC, JXA-8900-RL) the reflection electronic composition diagram on observable enamel test portion surface is shown in Fig. 7 (a).Form the high part (white portion of strip in the photo) of weisspiessglanz concentration in the enamel test portion, this part forms protuberance after the accelerated test, and it is big that surfaceness becomes.The comparative example 1 of the 3rd invention
In 1100-1400 ℃ of fusion, quenching in water obtains the vitrifying sinter to the glaze raw material that table 4 is formed in electric furnace.Vitrifying sinter 2kg and stone ball 4kg are joined in the pottery pot of 6 liters of volumes, pulverize in ball mill, make it all by 150 purposes sieve, the powder that obtains like this is as glaze.The glaze powder that obtains like this is as glaze C.
Secondly on the tabular metallographictest sheet of the cast iron of 100 * 100mm, apply the ground-coat enamel medicine with wet type glazing method, in 800-1100 ℃ of sintering, apply glaze A in heated condition with dry enamelling, again in 800-1100 ℃ of sintering, then in heated condition with dry enamelling coating glaze ℃, in 800-1100 ℃ of sintering, obtain the enamel test portion again.Can see that enamel test portion glaze C layer has yellowish color.
This enamel test portion is boiled in the NaOH of the 5wt% aqueous solution, flooded 3 hours, obtain the accelerated test test portion.
With the enamel test portion that obtains with quicken test portion and carry out the evaluation same with comparative example 1, the result of the mensuration of surfaceness, enamel test portion: Ra=1.6nm quickens test portion: Ra=10nm.The 3rd inventive embodiment 2
Add the weisspiessglanz of 1wt% in the glaze raw material that table 4 is formed, in 1100-1400 ℃ of fusion, quenching in water obtains the vitrifying sinter in electric furnace.Gained vitrifying sinter 2kg and stone ball 4kg are joined in the pottery pot of 6 liters of volumes, pulverize in ball mill, make it all by 150 purposes sieve, the powder that obtains like this is as glaze, and the glaze powder that obtains like this is as glaze D.
Secondly on the tabular metallographictest sheet of the cast iron of 100 * 100mm, apply the ground-coat enamel medicine with wet type glazing method, in 800-1100 ℃ of sintering, apply glaze A in heated condition with dry enamelling, again in 800-1100 ℃ of sintering, apply glaze D in heated condition with dry enamelling then, in 800-1100 ℃ of sintering, obtain the enamel test portion again.
This enamel test portion is boiled in the NaOH of the 5wt% aqueous solution, flooded 3 hours, obtain the accelerated test test portion.
With the enamel test portion that obtains with quicken test portion and carry out the evaluation same with comparative example 1, the result of the mensuration of surfaceness, enamel test portion: Ra=2.4nm quickens test portion: Ra=7.5nm.The 3rd inventive embodiment 3
Add the weisspiessglanz of 0.5wt% in the glaze raw material that table 4 is formed, in 1100-1400 ℃ of fusion, quenching in water obtains the vitrifying sinter in electric furnace.Gained vitrifying sinter 2kg and stone ball 4kg are joined in the pottery pot of 6 liters of volumes, pulverize in ball mill, make it all by 150 purposes sieve, the powder that obtains like this is as glaze, and the glaze powder that obtains like this is as glaze E.
Secondly on the tabular metallographictest sheet of the cast iron of 100 * 100mm, apply the ground-coat enamel medicine with wet type glazing method, in 800-1100 ℃ of sintering, apply glaze A in heated condition with dry enamelling, again in 800-1100 ℃ of sintering, be used for formula glazing method coating glaze E in heated condition then, in 800-1100 ℃ of sintering, obtain the enamel test portion again.
This enamel test portion is boiled in the NaOH of the 5wt% aqueous solution, flooded 3 hours, obtain the accelerated test test portion.
With the enamel test portion that obtains with quicken test portion and carry out the evaluation same with comparative example 1, the result of the mensuration of surfaceness, enamel test portion: Ra=2.2nm quickens test portion: Ra=5.8nm.
The observable surperficial enlarged view of each atomic force microscope (AFM) as Fig. 6 (b1) (b2) shown in, electron probe micro-analysis device (EPMA; NEC, JXA-8900-RL) the reflection electronic composition diagram on observable enamel test portion surface is shown in Fig. 7 (b).The 3rd inventive embodiment 4
Add the weisspiessglanz of 0.1wt% in the glaze raw material that table 4 is formed, in 1100-1400 ℃ of fusion, quenching in water obtains the vitrifying sinter in electric furnace.Gained vitrifying sinter 2kg and stone ball 4kg are joined in the pottery pot of 6 liters of volumes, pulverize in ball mill, make it all by 150 purposes sieve, the powder that obtains like this is as glaze.The glaze powder that obtains like this is as glaze F.
Secondly on the tabular metallographictest sheet of the cast iron of 100 * 100mm, apply the ground-coat enamel medicine with wet type glazing method, in 800-1100 ℃ of sintering, apply glaze A in heated condition with dry enamelling, again in 800-1100 ℃ of sintering, apply glaze F in heated condition with dry enamelling then, in 800-1100 ℃ of sintering, obtain the enamel test portion again.
This enamel test portion is boiled in the NaOH of the 5wt% aqueous solution, flooded 3 hours, obtain the accelerated test test portion.
With the enamel test portion that obtains with quicken test portion and carry out the evaluation same with comparative example 1, the result of the mensuration of surfaceness, enamel test portion: Ra=4.5nm quickens test portion: Ra=12nm.
Table 5
| The concentration of weisspiessglanz (wt%) | Outward appearance | ????Ra(nm) | ||
| Initial stage | After the accelerated test | |||
| Comparative example 1 | ????2 | Normally | 2.9 | 27 |
| Embodiment 1 | ????0 | Painted | 1.6 | 10 |
| Embodiment 2 | ????1 | Normally | 2.4 | 7.5 |
| Embodiment 3 | ????0.5 | Normally | 2.2 | 5.8 |
| Embodiment 4 | ????0.1 | Normally | 4.5 | 12 |
The result of the 3rd inventive embodiments is as shown in table 5, when making that wherein weisspiessglanz concentration is lower than 2wt%, can suppress the increase of accelerated test rear surface roughness.And, can not produce painted by adding weisspiessglanz.
According to the present invention, be regardless of the difference of we on making, reach the superiors' glaze layer surfaceness easily and be lower than 0.06 μ m.Reproducibility is good as a result for it, has to keep the performance that long-time back is removed crude removal easily, can be bath, tank, and washing basins etc. provide enamelware.
According to the present invention, even can provide the increase of life-time service surfaceness few, whenever, dirt is difficult for adhering to, and the enamelware that can remove simply with flowing water of the dirt that adheres to.Fig. 1: first inventive embodiment Fig. 2: first inventive embodiment Fig. 3: the condition of surface of the enamel test portion that contact pin type surface roughness measurement device (JIS-B0651) is measured
(a) Yi Qian enamel surface (comparative example 1)
(b) enamel surface of the present invention (embodiment 1) Fig. 4: the secondary electron photo on the observed enamel test portion of scanning electronic microscope (SEM) surface
(a) Yi Qian enamel surface (comparative example 1)
(b) enamel surface of the present invention (embodiment 1) Fig. 5: the condition of surface on the observed enamel test portion of atomic force microscope (AFM) surface
(a) Yi Qian enamel surface (comparative example 1)
(b) enamel surface of the present invention (embodiment 1) Fig. 6: the condition of surface on the observed enamel test portion of atomic force microscope (AFM) surface
(a1) Yi Qian enamel surface (comparative example 1)
(a2) after the enamel surface accelerated test before (comparative example 1)
(b1) enamel surface of the present invention (embodiment 3)
(b2) (embodiment 3) Fig. 7 after the surperficial accelerated test of enamel of the present invention: the reflection electronic on the observed enamel test portion of electron probe micro-analysis device (EPMA) surface is formed photo
(a) Yi Qian enamel surface (comparative example 1)
(b) enamel surface of the present invention (embodiment 3)
Below symbol among the figure is illustrated.
1: metal base
2: the ground-coat enamel medicine
3: the first glaze layers (pigmented layer milkiness glaze layer)
4: the second glaze layers (transparent glaze layer)
5: the first glaze layers (tint permanence milkiness glaze layer)
6: the second glaze layers (the transparent glaze layer of tint permanence)
7: the three glaze layers (transparent glaze layer)
21: medullary ray
22: enamel glaze laminar surface expanded view
Claims (50)
1. enamel system, this enamelware is first glaze layer that forms painted milkiness in metallic substrate surface, forms the enamelware of second glaze layer of the transparency more thereon, it is characterized in that the thickness of above-mentioned second glaze layer is more than the 0.5mm.
2. the enamelware of claim 1 is characterized in that, the thickness of above-mentioned first glaze layer is more than the 0.3mm.
3. the enamelware of claim 1 or 2 records is characterized in that, the thickness total of above-mentioned first and second glaze layers is lower than 2.5mm.
4. the enamelware of each record of claim 1-3 is characterized in that, the surfaceness of above-mentioned second glaze layer is measured with contact pin type surface roughness measurement device (JIS-B0651) and is lower than 0.06 μ m.
5. enamelware, this enamelware is first glaze layer that forms milkiness in metallic substrate surface, form second glaze layer of the painted transparency more thereon, form the enamelware of the transparency the 3rd glaze layer more thereon, it is characterized in that, the thickness of above-mentioned the second, the second glaze layer adds up to more than the 0.5mm.
6. the enamelware of claim 5 is characterized in that, the thickness of above-mentioned the 3rd glaze layer is more than the 0.15mm.
7. the enamelware of claim 5 or 6 records is characterized in that the thickness of above-mentioned first glaze layer is more than the 0.3mm.
8. the enamelware of claim 5-7 record is characterized in that the thickness of above-mentioned the first, the second, the 3rd glaze layer adds up to below the 2.5mm.
9. the enamelware of each record of claim 5-8 is characterized in that, the surfaceness on above-mentioned the 3rd glaze layer surface is measured with contact pin type surface roughness measurement device (JIS-B0651) and is lower than 0.06 μ m.
10. enamelware, this enamelware are the enamelwares that forms glaze layer in metallic substrate surface, it is characterized in that, the surface roughness Ra on above-mentioned glaze layer surface is lower than 0.06 μ m with contact pin type surface roughness measurement device (JIS-B0651) mensuration.
11. an enamelware, this enamelware are the enamelwares that forms glaze layer in metallic substrate surface, it is characterized in that the surface roughness Ra on above-mentioned glaze layer surface is determined at below the 0.05 μ m with contact pin type surface roughness measurement device (JIS-B0651).
12. an enamelware, this enamelware are the enamelwares that forms glaze layer in metallic substrate surface, it is characterized in that the surface roughness Ra on above-mentioned glaze layer surface is determined at below the 0.03 μ m with contact pin type surface roughness measurement device (JIS-B0651).
13. the enamelware of each record of claim 10-12 is characterized in that, does not contain emboliform material in above-mentioned glaze layer.
14. kind enamelware, this enamelware is first glaze layer that forms tint permanence in metallic substrate surface, form the enamelware of second glaze layer that does not contain particle-like substance again in above-mentioned first glaze layer surface, it is characterized in that the surface roughness Ra on the above-mentioned second glaze layer surface is measured with contact pin type surface roughness measurement device (JIS-B0651) and is lower than 0.06 μ m.
15. enamelware, this enamelware is first glaze layer that forms tint permanence in metallic substrate surface, form the enamelware of second glaze layer that does not contain particle-like substance again in above-mentioned first glaze layer surface, it is characterized in that the surface roughness Ra on the above-mentioned second glaze layer surface is determined at below the 0.05 μ m with contact pin type surface roughness measurement device (JIS-B0651).
16. enamelware, this enamelware is first glaze layer that forms tint permanence in metallic substrate surface, form the enamelware of second glaze layer that does not contain particle-like substance again in above-mentioned first glaze layer surface, it is characterized in that the surface roughness Ra on the above-mentioned second glaze layer surface is determined at below the 0.03 μ m with contact pin type surface roughness measurement device (JIS-B0651).
17. the enamelware of each record of claim 14-16 is characterized in that, above-mentioned second glaze layer is transparent.
18. the enamelware of each record of claim 10-17, it is the enamelware that forms glaze layer in metallic substrate surface, it is characterized in that, the contact angle of above-mentioned glaze layer or second glaze layer surface and water is lower than 30 °.
19. the enamelware of each record of claim 10-17, it is the enamelware that forms glaze layer in metallic substrate surface, it is characterized in that, the contact angle of above-mentioned glaze layer or second glaze layer surface and water is below 25 °.
20. the enamelware of each record of claim 10-17, it is the enamelware that forms glaze layer in metallic substrate surface, it is characterized in that, the contact angle of above-mentioned glaze layer or second glaze layer surface and water is below 20 °.
21. the enamelware of each record of claim 10-20 is characterized in that, above-mentioned enamelware is a bath.
22. the enamelware of each record of claim 10-20 is characterized in that, above-mentioned enamelware is a washing basin.
23. the enamelware of each record of claim 10-20 is characterized in that, above-mentioned enamelware is the bathroom building materials.
24. the enamelware of each record of claim 10-20 is characterized in that, above-mentioned enamelware is the kitchen wall dunnage.
25. the enamelware of each record of claim 10-20 is characterized in that, above-mentioned enamelware is the washing basin backboard.
26. the enamelware of each record of claim 10-20 is characterized in that, above-mentioned enamelware is the bath wall dunnage.
27. the enamelware of each record of claim 10-20 is characterized in that, above-mentioned enamelware is a tank.
28. the enamelware of each record of claim 10-20 is characterized in that, above-mentioned enamelware is a backstairs.
29. an enamelware, this enamelware are the enamelwares that forms surperficial glaze layer on metal base, it is characterized in that the weisspiessglanz concentration in the above-mentioned surperficial glaze layer is lower than 2wt%.
30. an enamelware, this enamelware are the enamelwares that forms surperficial glaze layer on metal base, it is characterized in that the weisspiessglanz concentration in the above-mentioned surperficial glaze layer is below 1.5wt%.
31. an enamelware, this enamelware are the enamelwares that forms surperficial glaze layer on metal base, it is characterized in that the weisspiessglanz concentration in the above-mentioned surperficial glaze layer is below 1wt%.
32. the enamelware of each record of claim 29-31, it is the enamelware that forms surperficial glaze layer on metal base, it is characterized in that the weisspiessglanz concentration in the above-mentioned surperficial glaze layer is more than the 0.001wt%.
33. the enamelware of each record of claim 29-31, it is the enamelware that forms surperficial glaze layer on metal base, it is characterized in that the weisspiessglanz concentration in the above-mentioned surperficial glaze layer is more than the 0.01wt%.
34. the enamelware of each record of claim 29-31, it is the enamelware that forms surperficial glaze layer on metal base, it is characterized in that the weisspiessglanz concentration in the above-mentioned surperficial glaze layer is more than the 0.1wt%.
35. an enamelware, this enamelware are to form the tint permanence glaze layer on metal base, form the enamelware of surperficial glaze layer more thereon, it is characterized in that the weisspiessglanz concentration in the above-mentioned surperficial glaze layer is lower than 2wt%.
36. an enamelware, this enamelware are to form the tint permanence glaze layer on metal base, form the enamelware of surperficial glaze layer more thereon, it is characterized in that the weisspiessglanz concentration in the above-mentioned surperficial glaze layer is below 1.5wt%.
37. an enamelware, this enamelware are to form the tint permanence glaze layer on metal base, form the enamelware of surperficial glaze layer more thereon, it is characterized in that the weisspiessglanz concentration in the above-mentioned surperficial glaze layer is below 1wt%.
38. the enamelware of each record of claim 35-37, it is to form the tint permanence glaze layer on metal base, forms the enamelware of surperficial glaze layer more thereon, it is characterized in that the weisspiessglanz concentration in the above-mentioned surperficial glaze layer is more than 0.001wt%.
39. the enamelware of each record of claim 35-37, it is to form the tint permanence glaze layer on metal base, forms the enamelware of surperficial glaze layer more thereon, it is characterized in that the weisspiessglanz concentration in the above-mentioned surperficial glaze layer is more than 0.01wt%.
40. the enamelware of each record of claim 35-37, it is to form the tint permanence glaze layer on metal base, forms the enamelware of surperficial glaze layer more thereon, it is characterized in that the weisspiessglanz concentration in the above-mentioned surperficial glaze layer is more than 0.1wt%.
41. the enamelware of each record of claim 35-40 is characterized in that, contains opacifying agent and pigment in the above-mentioned tint permanence glaze layer.
42. the enamelware of each record of claim 35-40 is characterized in that, above-mentioned surperficial glaze layer is transparent.
43. the enamelware of each record of claim 29-42 is characterized in that, above-mentioned enamelware is a bath.
44. the enamelware of each record of claim 29-42 is characterized in that, above-mentioned enamelware is a washing basin.
45. the enamelware of each record of claim 29-42 is characterized in that, above-mentioned enamelware is the bathroom building materials.
46. the enamelware of each record of claim 29-42 is characterized in that, above-mentioned enamelware is the kitchen wall dunnage.
47. the enamelware of each record of claim 29-42 is characterized in that, above-mentioned enamelware is the washing basin backboard.
48. the enamelware of each record of claim 29-42 is characterized in that, above-mentioned enamelware is the bath wall dunnage.
49. the enamelware of each record of claim 29-42 is characterized in that, above-mentioned enamelware is a tank.
50. the enamelware of each record of claim 29-42 is characterized in that, above-mentioned enamelware is a backstairs.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28983699A JP2001107266A (en) | 1999-10-12 | 1999-10-12 | Enameled product |
| JP289836/1999 | 1999-10-12 | ||
| JP291262/1999 | 1999-10-13 | ||
| JP29126299A JP2001003183A (en) | 1999-04-22 | 1999-10-13 | Enameled product |
| JP31188799A JP2001131775A (en) | 1999-11-02 | 1999-11-02 | Enameled product |
| JP311887/1999 | 1999-11-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1319684A true CN1319684A (en) | 2001-10-31 |
Family
ID=27337536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00134890 Pending CN1319684A (en) | 1999-10-12 | 2000-10-12 | Enamel products |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1319684A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098273A (en) * | 2014-07-15 | 2014-10-15 | 陕西科技大学 | Glass glaze for easy-breaking ampoule, and preparation method of glass glaze |
| CN108483917A (en) * | 2018-06-06 | 2018-09-04 | 无锡大塘复合材料有限公司 | A kind of improved enamel not adhering process method |
| 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 |
| CN112062469A (en) * | 2020-08-28 | 2020-12-11 | 浙江开尔新材料股份有限公司 | Bottom glaze material of stainless steel enamel plate and preparation method and application thereof |
-
2000
- 2000-10-12 CN CN 00134890 patent/CN1319684A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098273A (en) * | 2014-07-15 | 2014-10-15 | 陕西科技大学 | Glass glaze for easy-breaking ampoule, and preparation method of glass glaze |
| CN104098273B (en) * | 2014-07-15 | 2016-02-10 | 陕西科技大学 | A kind of glass glaze for easy cut ampule and preparation method thereof |
| CN108483917A (en) * | 2018-06-06 | 2018-09-04 | 无锡大塘复合材料有限公司 | A kind of improved enamel not adhering process method |
| CN108483917B (en) * | 2018-06-06 | 2021-03-23 | 无锡大塘复合材料有限公司 | Improved enamel non-stick process |
| 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 |
| CN112062469A (en) * | 2020-08-28 | 2020-12-11 | 浙江开尔新材料股份有限公司 | Bottom glaze material of stainless steel enamel plate and preparation method and application thereof |
| CN112062469B (en) * | 2020-08-28 | 2022-06-03 | 浙江开尔新材料股份有限公司 | Bottom glaze material of stainless steel enamel plate and preparation method and application thereof |
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