CN104691056A - Glass-ceramic and glass plates and heating plates and its manufacture - Google Patents
Glass-ceramic and glass plates and heating plates and its manufacture Download PDFInfo
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- CN104691056A CN104691056A CN201510058469.5A CN201510058469A CN104691056A CN 104691056 A CN104691056 A CN 104691056A CN 201510058469 A CN201510058469 A CN 201510058469A CN 104691056 A CN104691056 A CN 104691056A
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- sheet material
- glass
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- coating
- ceramic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
-
- 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24C—DOMESTIC STOVES OR RANGES ; DETAILS OF DOMESTIC STOVES OR RANGES, OF GENERAL APPLICATION
- F24C15/00—Details
- F24C15/10—Tops, e.g. hot plates; Rings
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Laminated Bodies (AREA)
- Surface Treatment Of Glass (AREA)
- Paints Or Removers (AREA)
Abstract
The application discloses contents of: (i) a glass-ceramic plate or glass plate having certain transparency, and the plate has two basically parallel main surfaces, and at least partial surface of the two main surfaces is fixed with a color coating; (ii) a heating plate formed by the said plate may be formed by the said plate, and specifically refers to a cooking range surface. The heating plate is arranged above a heating element, the surface, having coating, of the heating plate faces the heating element; the content also comprises (iii) the manufacture of the plate. The unique color coating with stable color is very impressive.
Description
The application is the division of the application for a patent for invention " glass-ceramic and glass plate, heating plate, and manufacture " that the application number that Ooo Corning submits to is 200580009435.1, the applying date is on September 25th, 2006.
Invention field
The present invention relates to glass-ceramic and glass plate, heating plate and manufacture method thereof.Specifically, the present invention relates to the cated glass-ceramic of tool and glass plate, particularly heating plate, and manufacture method.
Background of invention
The object of the invention is:
-there is glass-ceramic or the glass plate of certain transparency, these sheet materials have two substantially parallel interareas, described two interareas one of them be fixed wtih coloured coating on the surface at least partially;
-be made up of described sheet material or the heating plate that can be obtained by described sheet material, cooktop surface specifically.These heating plates are used for being arranged on above heating element heater, they have described coating facing to described heating element heater;
The manufacture of-described sheet material.
Sheet material of the present invention is transparent; In any case its transparency is all enough to the coloured coating making it possible to observe through their thickness them, and the feature of this sheet material is the special nature of their coloured coating.
Heating plate of the present invention is efficient especially, particularly has high efficiency especially for strict demand hereinafter described.
Describe the cooktop surface manufactured primarily of glass-ceramic or safety glass in prior art, in their D score face (or the back side or below), in the one side of heating element heater, namely deposit colored coating.
In No. 075, patent application EP-A-277, be usually used for carrying out decoration on the back side of the glass-ceramic of cooking or marked element by eddy-current heating.Do not describe described decoration or marked element in detail.
In No. 267 593, patent application EP-A-1, below describing, (lower side) has the transparent glass-ceramic plate of coloured coating.Described sheet material is applicable to eddy-current heating, even the composite heating of eddy-current heating and radiation heating.The glazing of described coloured coating metallic pigments, described metallic pigments self are optionally covered by organic coating (such as polyimides, polyamide, fluoride resin, organic siliconresin) on the surface in " heat ".
In No. 014, patent application EP-A-861, whole relative with the face being used for accepting kitchen utensils has can the skin of paint of high temperature resistant (preferably higher than 650 DEG C).But do not describe the definite character of described paint in detail.
No. 084 263, patent application US-A-2002/0 and No. 019 864, US-A-2003/0 describes transparent glass-ceramic as the cooking surface of radiation heating and safety glass base material.Comprise (US-A-2002/0 084 263) or do not comprise (US-A-2003/0 019 864) enamel coating above described base material.Below these base materials, namely towards that mask of radiant heater element, have that transmissive is ultrared has (particularly comprising the sol-gel layer of pigment) of different nature coating, these coatings are applicable to the region needing decoration, are more particularly be applicable in use stood temperature.
Apply for that No. 838 429, FR-A-2 describes and be used for the glass-ceramic of covering heating elements especially, at least one face of these sheet materials has at least one enamel solid and/or there is at least one deck skin of paint.Preferably below sheet material, there is skin of paint, unless it needs to have the thermal treatment zone.The degradation temperature of paint used, preferably higher than 350 DEG C, is generally 350-550 DEG C.It is preferred that described paint is based on one or more organic siliconresins, particularly preferably described paint comprises one or more silicone alkyds (one or more organic siliconresins by conjunction with one or more alkyd resins modifications).This paint also can comprise pigment, such as TiO
2.The mode of heating provided is eddy-current heating substantially.
In this context, the present inventor contemplates novel glass-ceramic and glass plate, and be fixed wtih coloured coating below these sheet materials, these sheet materials are effective especially in following properties:
-described coloured coating color stability in use;
-in use, the stability of the adherence of described coating and the anchorage to sheet material lower surface thereof;
-described coating to eddy-current heating (adopt up to 350 DEG C, final the temperature of peak value up to 500 DEG C) and halogen or the applicability of electrical heating elements (adopting the temperature of 650-700 DEG C) of radiation;
-engineering properties: the existence of described coating does not affect the engineering properties of described sheet material.Contrary, even observe the raising of described engineering properties.
Involved technical problem is this coating color stability at this temperature.The coating proposed about this technical problem is key of the present invention, finds surprisingly, although the character of this coating is inorganic from organically changing over, the above-mentioned all character of this coating is all fine.In conjunction with hereafter understanding this point better.
Summary of the invention
Therefore, according to a first aspect of the present invention, provide the glass-ceramic or glass plate with certain transparency, this sheet material has two substantially parallel interareas, be fixed wtih coloured coating on the surface at least partially one of in described two interareas, it is characterized in that, described coloured coating forms primarily of the mixture of following component: (i) guarantees its painted and inorganic filler that is mechanical enhancer, and the crosslinkable polyorganosiloxane resin of (ii) at least one, described polyorganosiloxane resin (almost) is not containing one or more precursors of one or more carbonaceous materials, described filler (i) is distributed in described crosslinkable silicone resin.
Second aspect present invention is the heating plate that (being used for) is arranged on above heating element heater, cooktop surface specifically, it is characterized in that, this heating plate is made up of above-mentioned sheet material, described sheet material (expection) make it have when mounted described coloured coating facing to described heating element heater.
A third aspect of the present invention is the manufacture view of above-mentioned plate, it is characterized in that the method comprises: the precursor plate of glass-ceramic or glass plate or this plate an interarea at least partially on the surface, deposit at least one deck and mainly comprise the layer of the mixture of following component: (i) guarantees its painted and inorganic filler that is mechanical enhancer, and the crosslinkable polyorganosiloxane resin of (ii) at least one, described polyorganosiloxane resin (almost) is not containing one or more precursors of one or more carbonaceous materials, described filler (i) is distributed in described crosslinkable silicone resin.
Detailed Description Of The Invention
In fact first object of the present invention is:
-be suitable as the precursor plate of the sheet material of heating plate;
-the sheet material being suitable as heating plate that can be obtained by described sheet material.
In other words:
Sheet material; Namely have complete part (full element), this sheet material has two approximately parallel interareas (its thickness is less than the surface of described interarea);
Its material is glass-ceramic or glass; Described glass can have various character.Precursor plate can be glass precursor, can be glass-ceramic precursor glass, or safety glass glass precursor (will carry out heat tempering process)." finally " sheet material can be safety glass or glass;
There is certain transparency: completely transparent or fully transparent, thus their coloured coating (seeing below) can be observed through their thickness;
Be fixed with coloured coating on the surface at least partially one of in their two interareas: described material coating expection will be positioned in this one side of heating element heater, can observe through the thickness of sheet material.Described colour-wash is the colourless resin based on being filled with one or more colouring agents.
Described glass-ceramic or glass plate are precursors, are not also precursor, it is characterized in that the originality of their coloured coating, and described sheet material can exist in a variety of manners relative to the relation of described coating:
-there is sheet material without heat treated described coloured coating;
-there is sheet material through heat treated described coloured coating, the whole surface of described coating was all in more or less violent mode, evenly or unevenly carried out process.
According to a kind of variant, glass precursor (glass-ceramic precursor or safety glass precursor) and coating thereof all carried out described process.
Therefore, in product of the present invention, there is a large amount of variants.
According to the first variant, sheet material of the present invention is:
The glass-ceramic of-mentioned kind, or
The glass plate (be called as the glass of " finally " glass, safety glass, or be called as glass-ceramic precursor glass, the safety glass glass precursor of " precursor " glass, glass precursor also needs to heat-treat) of-mentioned kind,
Its starting color coating forms primarily of the mixture of following component: (i) guarantees its painted and inorganic filler that is mechanical enhancer, and (ii) at least one crosslinkable silicone resin, described polyorganosiloxane resin (almost) is not containing one or more precursors of one or more carbonaceous materials, and described filler (i) is distributed in described crosslinkable silicone resin.
This starting color coating needs to heat-treat, and this heat treatment, at least in part under more or less violent condition, is carried out in manufacturing works or in the house of described sheet material user.Described heat treatment can only be carried out coating, or carries out together with coating whole glass precursor plate.It will be appreciated by those skilled in the art that, the heat treatment of gentleness mainly can guarantee the crosslinked of the resin on final category of glass sheet material or glass-ceramic class sheet material, and violent heat treatment mainly can guarantee the resin crosslinks then pyrolysis on final category of glass sheet material or glass-ceramic class sheet material, or guarantee the heat treatment of the crosslinked of described resin and pyrolysis and described glass precursor class sheet material simultaneously.
After all variants listing sheet material of the present invention, the character of two kinds of components (crosslinkable resin and inorganic filler) of described primary coat will be described herein.
According to second variant, sheet material of the present invention is:
The glass-ceramic of-mentioned kind, or
Glass (glass or safety glass are called as " final the glass ") plate of-mentioned kind, it obtains (being called as the glass-ceramic of " final glass " or the sheet material of glass) by carrying out above-mentioned heat treatment to sheet material; In other words, its coloured coating (at least in part, be made up of the mixture of following component preferably fully): (i) guarantees its painted and inorganic filler that is mechanical enhancer, and the crosslinkable polyorganosiloxane resin of (ii) at least one, described polyorganosiloxane resin (almost) is not containing one or more precursors of one or more carbonaceous materials, and described filler (i) is distributed in described crosslinkable silicone resin.
Here, described polyorganosiloxane resin (at least in part) is crosslinked, and is only crosslinked.
According to preferred embodiment, described resin all (only) is crosslinked.
According to another embodiment, described resin (only) is for partial cross-linked.In other parts, resin is not heat-treated, and still keeps " initially " state.Such as it is contemplated that the region removing resin of will not heat-treat from it.
According to another embodiment, described resin is partial cross-linked and partial thermal decomposition, is namely partially converted into porous inorganic substrate.Therefore from feature, coloured coating of the present invention is organically (resin be only cross-linked) and inorganic (resin of pyrolysis).
Obviously, the second variant comprises another kind of embodiment, and wherein said coloured coating exists with three kinds of forms: have crosslinked resin, has nonheat-treated resin, has the resin of pyrolysis.
According to the third variant, sheet material of the present invention is:
The glass-ceramic of-mentioned kind, or
The glass (glass or safety glass are called " final glass ") of-mentioned kind,
It obtains (being called as the glass-ceramic of " glass precursor " or " final glass " or the sheet material of glass) by carrying out above-mentioned heat treatment to sheet material; In other words, its coloured coating (at least in part, be made up of the mixture of following component preferably fully): (i) guarantees the inorganic filler of its color and mechanical enhancer, and (ii) silicon-dioxide-substrate porous inorganic substrate, this matrix (almost) is not containing one or more carbonaceous materials, and described filler (i) is distributed in described matrix.
Here, described coating is inorganic coating at least partly.
According to one preferred embodiment, all pyrolysis of described resin, therefore find its whole mineralising.
According to another embodiment, described resin is only subject to the heat treatment of part, only generating portion pyrolysis.In other parts, resin is not heat-treated, and still keeps " initially " state.Such as it is contemplated that, need not to be subject to the resin removing in heat treated region.
According to another embodiment, this situation described above, and resin portion, by pyrolysis, is partially converted into inorganic matrix, was only partial cross-linked.Therefore from feature, coloured coating of the present invention is organic and inorganic.
Clearly, the third variant comprises the embodiment that another kind belongs to above-mentioned three element type, and wherein coloured coating exists with three kinds of forms: thermal decomposed resins, nonheat-treated resin and crosslinked resin.
The kind of the invention described above sheet material is included into the 4th kind of variant, and this variant is the artificial board being called as " mixing " sheet material.A part for described mixed type coloured coating is made up of the mixture of following component: (i) guarantees its painted and inorganic filler that is mechanical enhancer, and the crosslinkable polyorganosiloxane resin of (ii) at least one, described polyorganosiloxane resin (almost) is not containing one or more carbonaceous materials, also not containing one or more precursors of one or more carbonaceous materials, described filler (i) is distributed in described crosslinkable silicone resin; Another part of this coating is made up of the mixture of following component: (iii) guarantees its painted and inorganic filler that is mechanical enhancer, and (iv) silicon-dioxide-substrate porous inorganic substrate, this matrix (almost) is not containing one or more carbonaceous materials, and described inorganic filler (iii) is distributed in this matrix.
Described filler (i) and (iii) can be identical or different kinds; Described inorganic matrix (iv) is obtained by crosslinked resin (iii) pyrolysis, or is obtained by other resin pyrolysis, and this depends on method used.
Known sheet material of the present invention mainly can be divided into following a few class:
A) there is the sheet material (having or do not have precursor base substrate (basesubstrate)) of the crosslinkable resin of filling,
B) there is the sheet material of the resin of crosslinked filling,
C) there is the sheet material of the resin of the filling of pyrolysis,
D) there is the sheet material of the potting resin of only partial cross-linked, other parts pyrolysis.
Comprise the sheet material of the present invention of the crosslinkable resin of the resin being filled with the crosslinked resin of filling and/or the filling of pyrolysis, will be not described in detail hereinafter.Those skilled in the art can imagine their existence easily in conjunction with the description of the following sheet material to other kind.
Therefore, above-mentioned a) the class base substrate it being combined with the crosslinkable resin of filling can be:
The precursor plate of-glass-ceramic precursor glass (" green glass "), or the precursor plate of safety glass glass precursor (carrying out tempering by heat treatment);
-glass-ceramic, the sheet material of safety glass or glass.
From feature, the crosslinkable resin of described filling comprises:
-as filler be used for guarantee its painted and inorganic filler that is mechanical enhancer.The filler (color filters) of identical type can guarantee the mechanical enhancer (adherence of coating, fixing of coating, the problem of appearance of coat and wherein fracture propagation) of required color and expection.According to another variant, also can use two kinds of fillers: for (colourless) filler of mechanical enhancer, and for painted other fillers (being generally coloring pigment).Also these coloring pigments can be combined with colored mechanical enhancer filler in addition.These fillers are well known by persons skilled in the art.They add in described crosslinkable resin effectively to measure;
-in the initial substrate be made up of at least one crosslinkable silicone resin, described resin is not substantially containing one or more precursors of one or more carbonaceous materials.One or more this kind of resin-bonded in the mixture.Its () is polysiloxanes resinoid: its () crosslinkable, can mineralising.
-this crosslinkable resin (almost) is not containing one or more carbonaceous materials: the colour stability can guaranteeing described coating under these conditions.
This condition does not comprise the siloxanes alkyd resins of application described in FR-A-2838429.
According to the intrinsic property of above-mentioned each component of the crosslinkable resin of described filling, this resin can form the coloured coating of sheet material effectively, and this coating is suitable for being heated by induction and halogen or radiant heater element.
Base material normally glass-ceramic sheet material, safety glass sheet material or the glass board material of above-mentioned b), c) and d) class sheet material.
From feature, the resin of described crosslinked filling comprises:
The filler of-mentioned kind: more particularly, this filler is easy to make coating have required color, and can slow down and even prevent spreading of crackle;
-described filler distribution is in the crosslinked initial base-material of mentioned kind.
Described crosslinked polyorganosiloxane resin (substantially), not containing one or more carbonaceous materials, does not also contain one or more precursors of one or more carbonaceous materials.Due to not containing one or more carbonaceous precursor, carry out crosslinkedly can not producing one or more carbonaceous materials, in addition, any further heat treatment (being unexpected or deliberate) all can not produce one or more carbonaceous materials.Thus the stability of color with temperature can be guaranteed.
There is (almost) not containing one or more carbonaceous materials and not containing the sheet material of the kind (above-mentioned b) class) of the color resin of one or more crosslinked polyorganosiloxane resins of the precursor of one or more carbonaceous materials, can more effectively for eddy-current heating.In the examples below, examine the colour stability of this kind of coloured coating, go back the described coating of quantitatively evaluating to the beneficial effect of sheet material engineering properties.
From feature, the resin of the filling of described pyrolysis comprises:
The filler of-mentioned kind: these fillers are always suitable for making coating have required color, also can slow down and even stop the extension of crackle;
-described filler distribution is in silicon-dioxide-substrate porous inorganic substrate, and this matrix (almost) is not containing one or more carbonaceous materials.
This inorganic matrix can pyrogenically prepared by described crosslinkable silicone resin.This inorganic matrix (almost) is not containing one or more carbonaceous materials, and described resin (almost) is not containing one or more precursors of one or more carbonaceous materials.
There is this kind of (above-mentioned c) class) sheet material of inorganic color coating (this coating (almost) is not containing one or more carbonaceous materials (containing the organic material of any trace)), can more effectively use halogen or radiant heater element to heat.Examine the colour stability of this kind of coloured coating in the examples below.
D) class sheet material comprises the coloured coating of mixed type, and part is b) class as above, and part is c) class as above.
The component of the coloured coating of sheet material of the present invention (particularly a), b), c) or d) class) will be described in complete nonrestrictive mode below.
It is preferred that a part of inorganic filler has layer structure.Thus make coating obtain caking property, the generation of crackle can be resisted.
It is preferred that in crosslinked or uncrosslinked at least one polyorganosiloxane resin, in the cumulative volume of described filler and described at least one resin for benchmark, the volume content of described filler is 10-60 volume %.When lower than this content, described filler will be difficult to guarantee mechanical enhancer usually.When higher than this content, described filler cannot leave enough volumes for described resin usually.Entirety will no longer include adherence, therefore no longer include mechanical enhancer.It is still further preferred that with the cumulative volume of described filler and described at least one resin for benchmark, the volume content of described filler is 15-30 volume %.
About at least one polyorganosiloxane resin, illustrate, when described resin is uncrosslinked, its (almost) be not containing one or more precursors of one or more carbonaceous materials, when it is crosslinked time, its (almost), not containing one or more carbonaceous materials, does not also contain one or more precursors of one or more carbonaceous materials; Be obtain this hypothesis by described uncrosslinked resin crosslinks according to described crosslinked resin, this is rational really.The purity of described crosslinked or uncrosslinked at least one polyorganosiloxane resin is preferably at least 90 % by weight, and most preferably purity is at least 95 % by weight.Use the resin with maximum purity, maximum colour stability can be made it have.
It is preferred that there is phenyl, methyl, ethyl, propyl group and vinyl segment in the chemical formula of described polyorganosiloxane resin, it is still further preferred that comprise phenyl and/or methyl moiety.It is preferred that resin is selected from:
-dimethyl silicone polymer,
-polydiphenylsiloxane,
-phenyl methyl siloxane polymer,
-dimethyl siloxane-diphenylsiloxane copolymer.
Regardless of the definite character of described resin, usually because its structural formula comprises SiOH and/or SiOMe group, be therefore crosslinkable.Take gross weight as benchmark, the amount of these groups is usually up to 1-6 % by weight.
The weight average molecular weight (Mw) of described polyorganosiloxane resin is generally 2,000-300,000 dalton.
Specially suitable resin is such as (but being not limited to) Dow
804,805,806,808,840,249,409HS and 418HS resin, purchased from Rhodia's
6405 and 6406 resins, purchased from General Electric Silicone's
resin and purchased from Wacker Chemie GmbH's
604 resins.
The coloured coating of sheet material of the present invention is (particularly based on the crosslinkable polyorganosiloxane resin of at least one, or based on the polyorganosiloxane resin that at least one is cross-linked, or based on the polyorganosiloxane resin of at least one pyrolysis, or to be cross-linked based at least one with the hybrid resin of pyrolysis) thickness be generally 1-100 micron, be preferably 5-50 micron.
Second object of the present invention will be described below: use above-mentioned b), c) or the d) heating plate that forms of class sheet material, cooktop surface specifically.Described sheet material is the top that (or expection is) is used for being arranged on heating element heater, and during installation, these sheet materials have one of coloured coating facing to described heating element heater.
Above-mentioned b) class sheet material can especially effectively for eddy-current heating.Their coating is very stable, is more particularly colour stable.Their engineering properties is strengthened by described coating.In addition, these sheet materials can stand temperature peak and can not produce any adverse effect.
Above-mentioned c) class sheet material can heating especially effectively for using halogen or radiation electric element to carry out.Their coating is very stable, is more particularly colour stable.
Above-mentioned d) class sheet material can especially effectively for Hybrid Heating.This coating has enough stability, specifically colour stability, can be used for various heating element heater.
B all above), c) all can be obtained by identical a) based plate (there is precursor coating) further with d) based plate.
In the second object of the present invention, preferably above-mentioned heating plate is used as the cooktop surface of induction heating cooking goods.
Finally the third object of the present invention will be described: the method manufacturing described sheet material.
No matter which kind of sheet material (glass-ceramic, armorplate glass or glass plate, glass-ceramic precursor glass or safety glass glass precursor are the precursor plate of material), described method is all included in the layer of upper at least partially at least one mixture primarily of following component of deposition composition of the interarea of described sheet material: (i) guarantees its painted and filler that is mechanical enhancer, and (ii) (almost) be not containing at least one crosslinkable silicone resin of one or more precursors of one or more carbonaceous materials, described filler (i) is distributed in this resin.
Described layer mainly comprises described mixture ((i)+(ii)), but it also can comprise other components of at least one, such as diluent.
This deposition process is implemented by any technology of the person's character being suitable for the layer (polyorganosiloxane resin of filling) that will be deposited.Specifically, described layer deposits by brushing deposition, blade coating deposition, spraying (spraying) deposition, electrostatic precipitation, immersion deposition, curtain deposition, serigraphy.But be not limited to these technology.It is preferred that the polyorganosiloxane resin of described filling is deposited by serigraphy.
The content of described sheet material as above, is here suitable for too, preferably:
-at least partially inorganic filler there is layer structure; And/or
The purity of-described at least one crosslinkable silicone resin is at least 90 % by weight, is most preferably at least 95 % by weight.
Other details of each component of the above-mentioned layer (above-mentioned coating) about deposition, are here suitable for too.
(glass-ceramic, safety glass or glass) sheet material or (rigidifying to be heated of glass-ceramic precursor glass or safety glass glass precursor) precursor plate of at least one layer described in deposition is coated with form the precursor plate being applicable to the sheet material of cooktop surface of the present invention.Therefore this sheet material can in factory even user house in operated.This is above-mentioned a) class sheet material.It is heat-treated; Only at least one layer described is heat-treated, or at least one layer described and precursor plate are heat-treated simultaneously.
In the case of the latter, method of the present invention comprises:
-deposition at least one layer described;
-heat-treat under certain conditions, described condition guarantees described (glass-ceramic precursor glass or safety glass glass precursor) precursor plate to be converted into (glass-ceramic or safety glass) sheet material, and guarantee the layer of one or more layers deposition described is cross-linked, and make its () fixing and pyrolysis.
Described heat treatment is violent heat treatment (ceramic or heating tempering, this is well known by persons skilled in the art), makes the layer deposited force pyrolysis occurs.Therefore make the polyorganosiloxane resin deposited that the mineralising of 100% occurs.
The violent heat treatment of identical type can be carried out, it is only acted on be deposited at least one layer on glass-ceramic or glass plate (safety glass or glass).
Known c) class sheet material of the present invention is obtained like this.
Pyrolysis, usually in baking oven or under ultrared effect, is carried out at higher than the temperature of 400 DEG C.
In another case, carried out gentle heat treatment, this heat treatment only acts on the layer of at least one deposition described.In the case, method of the present invention comprises:
-on glass-ceramic or glass (glass or safety glass) plate, deposit at least one layer described;
-to heat-treat under certain condition, described heat-treat condition is guaranteed the crosslinked of the layer of described one or more deposition and described crosslinked layer is fixed on described sheet material.
This gentle heat treatment is undertaken by any method, and thermal current heats, uses the radiation heating of infra-red radiation and so on specifically, or passes through the such electrical heating method of heating using microwave, eddy-current heating, high-frequency heating and radiation heating.The sheet material of above-mentioned b) type is obtained by this gentle heat treatment.
Finally, known sheet material of the present invention can have mixed type coating (above-mentioned d) based plate).The sheet material of known mentioned kind obtains by following steps:
-on glass-ceramic or glass (glass or safety glass) plate, deposit at least one layer described; Then
-at least one layer described is heat-treated, first described heat treatment carried out under (gentleness) condition, described condition guarantees that the layer of described one or more deposition is cross-linked, and this layer (crosslinked) is fixed on sheet material, then only heat-treat a part for described one or more fixing crosslinked layer under certain (acutely) condition, described violent condition can guarantee described one or more fixing layer pyrolysis.
Above-mentioned heat treatment comprises two steps.These steps can be carried out according to various variant.The first step can be carried out in factory.Then can sell the sheet material of the polysiloxane coating with crosslinked filling.Then, in the house of user, in the first process used, the described coating relative with halogen or radiant heater element, by pyrolysis, forms the sheet material with mixed type coating.Be readily appreciated that, this mixed type coating directly can obtain in factory.Specifically, obtained sheet material can only have the coating surface of 50% to be crosslinked, and other 50% is pyrolysis.
But also can obtain in the present invention have different coating (their filler is different and/or their material resin is different: character or (with) ratio is different) the sheet material of this mixed type.The regional of sheet material deposits the coating that these are different, then various heat treatment is carried out to them.
Those skilled in the art it can also be appreciated that also can obtain the sheet material of the present invention with crosslinkable resin similarly, is filled with the resin of the crosslinked resin of filling and/or the filling of pyrolysis in described crosslinkable resin.After deposited described resin, all surface of sheet material is not heat-treated.The region at least partially of this sheet material still keeps " initially " state.If will remove described uncrosslinked resin after this, peel resin off at least one region described, this method is highly profitable.
In any case now further disclose the sheet material (such as the character of filler used and/or resin is uneven, uneven in conjunction with the content of filler) of the uneven composition with described kind, this also forms a part of the present invention.
Which kind of method no matter is adopted to manufacture sheet material, now it is emphasized that their primary coat has unexpected performance.
Next by following nonrestrictive embodiments, product of the present invention and method will be described.
Embodiment
Embodiment 1:
Manufacture whitewash composition (being expressed as A in the following table) by the following method:
By 10 grams of Dow
249 silicone polymer particles are dissolved in 10 grams of Dow
in 840 organic siliconresins (the polymer toluene solution of 60%).This course of dissolution is completed by stirring at 80 DEG C.
After cooling, 7.46 grams had the coated interference pigment of layer structure
123 (Merck) and 3.73 grams of TiO
2rL628 (Ferro Couleurs France S.A.) adds in this solution, and is mixed to evenly.
With scraper (" blade coating "), said composition layer paving is applied on sheet glass (Corning1737 – 75x 25x 1.1 millimeters), then 250 DEG C of polymerizations 1 hour, the dry film of obtained thick about 25 microns.
Embodiment 1'(comparative example)
Also knife coating is used to be applied in by silicone composition (representing with C in following table) alkyd modified for commercially available whitewash on sheet glass (Corning 1737 – 75x 25x1.1 millimeter), then 250 DEG C of polymerizations 1 hour, the dry film of obtained thick about 25 microns.
In static oven, carried out thermal aging test under the condition shown in following table 1 after, the CS3 spectrophotometer (D65 light source/observe the angles of 10 °) of Applied Chroma Systems is used to record color dot x, y by reflexing to the reverberation had on the face of sample coatings:
table 1
| Thermal aging | x-A | Y-A | x-C | y-C |
| Reference (non-ageing) | 0.3161 | 0.3344 | 0.3182 | 0.3370 |
| 100 DEG C/2 hours | 0.3169 | 0.3352 | 0.3186 | 0.3374 |
| 200 DEG C/2 hours | 0.3159 | 0.3343 | 0.3204 | 0.3391 |
| 300 DEG C/2 hours | 0.3163 | 0.3346 | 0.3254 | 0.3415 |
| 400 DEG C/2 hours | 0.3168 | 0.3349 | 0.3228 | 0.3389 |
Measure and find, there is the sample of the coating being expressed as C after institute's temp. displaying function ageing, naked eyes its color visible become yellow, lark (in all samples C, x
max-x
min: 0.0084, y
max-y
min: 0.0045).
The sample with coating A of the present invention almost do not have under various aging condition variable color (in all samples A, x
max. – x
min: 0.0010, y
max.-y
min: 0.0009).
All these samples (non-ageing or ageing) have good glass-coating adhesion, and coating self has good caking property, meets the character that this application is pursued.
Embodiment 2:
Manufacture whitewash composition by the following method:
By 40 grams of Dow
249 silicone polymer particles are dissolved in 18 grams of Exxon purchased from Exxon MobilChemical
in 100 solvents.Be dissolved in 80 DEG C to carry out, stir during dissolving.
After cooling, by 29.1 gram of 325 object muscovite (muscovite mica) (CMMP:Comptoir desMin é raux et Matieres Premieres) and 14.6 grams of RL628TiO
2(Ferro Couleurs France S.A.) adds in this solution, is mixed to evenly.By serigraphy (silk screen: 90 strands/centimetre), said composition is applied on transparent glass-ceramic substrates (Eurokera), then 250 DEG C of polymerizations 1 hour, the dry film of obtained thick about 15 microns.
In static oven, carried out thermal aging test under the condition shown in following table 2 after, use the CS3 spectrophotometer (D65 light source/observe the angles of 10 °) of Applied Chroma Systems by reflex to there is sample coatings glass-ceramic face on reverberation record color dot x, y:
Table 2
| Thermal aging | x | y |
| Reference (non-ageing) | 0.3371 | 0.354 |
| 330 DEG C/475 hours | 0.3375 | 0.3548 |
| 400 DEG C/15 hours | 0.3382 | 0.3555 |
| 510 DEG C/9 hours | 0.3453 | 0.3616 |
| 700 DEG C/20 hours | 0.3382 | 0.354 |
Under these thermal aging conditions, observe sample have very trickle variable color.
All these samples (non-ageing or ageing) have good glass-coating adhesion, and coating self has good caking property, meets the character that this application is pursued.
By the sample of non-ageing and 400 DEG C of ageings 15 hours with 510 DEG C of ageings sample of 15 hours mechanical resistance with not containing the glass-ceramic substrates of coating mechanical resistance compared with, comparing is that classical measurement according to rupture modulus (MOR) carries out.
Test carries out on the disc sample of diameter 32 millimeters, and this sample is polished to 2.1 millimeters.On disk, apply filler, below coloured coating is positioned at, this disk is placed on the support of three legs.Contact is guaranteed with the ball of diameter 1.79 millimeters.The decrease speed of contact point is 0.3 mm/min.Assuming that Poisson's coefficient is 0.2, calculate MOR.
Following result illustrates, when sample has white coating of the present invention, comprise DEG C thermal aging through 400 DEG C and 510, relative to the glass-ceramic substrates of uncoated, its MOR increases significantly.
| MOR (MPa) | |
| The base material (14 samples) of uncoated: | 208±71 |
| There is the base material (8 samples) of white coating: | 243±68 |
| At 400 DEG C of ageings base material (5 samples) with white coating of 15 hours: | 271±54 |
| At 510 DEG C of ageings base material (6 samples) with white coating of 9 hours: | 259±66 |
Embodiment 3:
Manufacture metallized encrimson composition by the following method:
By 48 grams of Dow
249 silicone polymer particles are dissolved in 23.5 grams of Exxon purchased from Exxon MobilChemical
in 100 solvents.This is dissolved in 80 DEG C and carries out, and stirs.
After cooling, by 36.9 grams
524 (Merck) coated interference pigment adds in this solution, and is stirred to evenly.
By serigraphy (silk screen: 43 strands/centimetre), said composition is applied on transparent glass-ceramic substrates (Eurokera), then 250 DEG C of polymerizations 1 hour, the dry film of obtained thick about 35 microns.
In static oven, carried out thermal aging test under the condition shown in following table 3 after, use the CS3 spectrophotometer (D65 light source/observe the angles of 10 °) of Applied Chroma Systems by reflex to there is sample coatings glass-ceramic face on reverberation record color dot x, y:
Table 3
| Thermal aging | x | y |
| Reference (non-ageing) | 0.4194 | 0.3303 |
| 330 DEG C/475 hours | 0.4191 | 0.332 |
| 400 DEG C/15 hours | 0.4173 | 0.332 |
| 510 DEG C/9 hours | 0.4171 | 0.3354 |
| 700 DEG C/20 hours | 0.4203 | 0.3365 |
Under these thermal aging conditions, observe sample have very little variable color.
All these samples (non-ageing or ageing) have good glass-ceramic-coating adhesion, and coating self has good caking property, meets the character that this application is pursued.
Embodiment 4:
In order to obtained golden yellow (A), black (B), grey (C) coating, manufacture composition by the following method:
a: by 48 grams of Dow
249 silicone polymer particles are dissolved in 23.4 grams of Exxon purchased from ExxonMobil Chemical
in 100 solvents.This is dissolved in 80 DEG C and carries out, and stirs during dissolving.
After cooling, by 36.7 grams
502 coated interference pigments (Merck) add in solution, are mixed to evenly.
b: by 48 grams of Dow
249 silicone polymer particles are dissolved in 20.9 grams of Exxon purchased from ExxonMobil Chemical
in 100 solvents.This is dissolved in 80 DEG C and carries out, and stirs during dissolving.
After cooling, by 9.7 grams of graphite (granularity 2 microns) (Aldrich), 9.7 grams of talcums (granularity 10 microns) (Aldrich) and 26 grams of FA1204 black pigments (Pemco Brugge N.V.) add in this solution, are mixed to evenly.
c: by 48 grams of Dow
249 silicone polymer particles are dissolved in 22.2 grams of Exxon purchased from ExxonMobil Chemical
in 100 solvents.This is dissolved in 80 DEG C and carries out, and stirs during dissolving.
After cooling, by 36.8 grams
123 coated interference pigments (Merck) and 2.3 grams of V7709 black pigments (Ferro Couleurs France S.A.) add in solution, are mixed to evenly.
By serigraphy (silk screen: 90 strands/centimetre), these compositions are applied on transparent glass-ceramic substrates (Eurokera).250 DEG C of polymerizations 1 hour, obtain the dry film of thick about 15 microns.
Then the obtained sheet material of the present invention being highly suitable for eddy-current heating.
Embodiment 5:
Encrimson composition has been manufactured according to method similar to Example 3.
By serigraphy (silk screen: 120 strands/centimetre), said composition is applied on transparent glass-ceramic precursor glass baseplate (Eurokera).Carry out the polymerization of coating and the ceramic of glass by following heating process simultaneously:
-in 10 minutes, be warming up to 685 DEG C,
-keep 20 minutes at 685 DEG C,
-in 25 minutes, be warming up to 930 DEG C,
-keep 20 minutes at 930 DEG C,
-cool rapidly.
Obtained glass-ceramic sample has the red inorganic coating of about 10 micron thickness.These samples have good glass-ceramic-coating adhesion, and coating self has good caking property, have noticeable colour stability, meet the character that this application is pursued.
Claims (20)
1. there is glass-ceramic or the glass plate of certain transparency, this sheet material has two substantially parallel interareas, be fixed wtih coloured coating on the surface at least partially one of in described two interareas, it is characterized in that, described coloured coating forms primarily of the mixture of following component: (i) guarantees its painted and inorganic filler that is mechanical enhancer, and (ii) at least one crosslinkable silicone resin, described polyorganosiloxane resin does not contain or hardly containing the precursor of carbonaceous material, described filler (i) is distributed in described crosslinkable silicone resin.
2. there is glass-ceramic or the glass plate of certain transparency, this sheet material has two substantially parallel interareas, be fixed wtih coloured coating on the surface at least partially one of in described two interareas, this sheet material can by heat-treating obtained to sheet material according to claim 1, it is characterized in that, described coloured coating is main, at least in part, preferably all be made up of the mixture of following component: (i) guarantees its painted and inorganic filler that is mechanical enhancer, and the polyorganosiloxane resin that (ii) at least one is crosslinked, described polyorganosiloxane resin does not contain or contains carbonaceous material hardly, and not containing the precursor of carbonaceous material, described filler (i) is distributed in described crosslinked polyorganosiloxane resin.
3. there is glass-ceramic or the glass plate of certain transparency, this sheet material has two substantially parallel interareas, be fixed wtih coloured coating on the surface at least partially one of in described two interareas, this sheet material can obtain by heat-treating the sheet material described in claim 1 or 2, it is characterized in that, described coloured coating is main, at least in part, preferably all be made up of the mixture of following component: (i) guarantees its painted and inorganic filler that is mechanical enhancer, and (ii) silicon-dioxide-substrate porous inorganic substrate, this matrix does not contain or contains carbonaceous material hardly, described filler (i) is distributed in described matrix.
4. there is glass-ceramic or the glass plate of certain transparency, this sheet material has two substantially parallel interareas, be fixed wtih coloured coating on the surface at least partially one of in described two interareas, this sheet material can by heat-treating obtained to the sheet material described in claim 1 or 2, it is characterized in that, a part for described mixed type coloured coating is made up of the mixture of following component: (i) guarantees its painted and inorganic filler that is mechanical enhancer, and the polyorganosiloxane resin that (ii) at least one is crosslinked, this resin does not contain or contains carbonaceous material hardly, and not containing the precursor of carbonaceous material, described filler (i) is distributed in described resin, other parts of this coating are made up of the mixture of following component: (iii) guarantees its painted and inorganic filler that is mechanical enhancer, and (iv) silicon-dioxide-substrate porous inorganic substrate, this matrix does not contain or contains carbonaceous material hardly, described filler (iii) is distributed in described matrix.
5. the sheet material according to any one of claim 1-4, is characterized in that, described filler at least partially there is layer structure.
6. the sheet material according to any one of claim 1-5, is characterized in that, the volume content of the described filler be mixed in described crosslinked or uncrosslinked at least one polyorganosiloxane resin is 10-60 volume %, is preferably 15-30 volume %.
7. the sheet material according to any one of claim 1-6, is characterized in that, the purity of described crosslinked or uncrosslinked at least one polyorganosiloxane resin is at least 90 % by weight, is most preferably at least 95 % by weight.
8. the sheet material according to any one of claim 1-7, is characterized in that, described polyorganosiloxane resin is selected from:
Dimethyl silicone polymer,
Polydiphenylsiloxane,
Phenyl methyl siloxane polymer,
Dimethyl siloxane diphenylsiloxane copolymer.
9. the sheet material according to any one of claim 1-8, is characterized in that, the thickness of described coloured coating is 1-100 micron, preferred 5-50 micron.
10. heating plate, specifically will be arranged on the cooktop surface above heating element heater, it is characterized in that, the sheet material of this heating plate according to any one of claim 2-9 is formed, when mounted, make to have described coloured coating facing to described heating element heater.
11. heating plates as claimed in claim 10, are used as cooktop surface in the goods being undertaken cooking by eddy-current heating.
12. 1 kinds of methods, the sheet material be used for according to any one of manufacturing claims 1-11, it is characterized in that, the method comprises: the going up at least partially of interarea of the precursor plate of glass-ceramic or glass plate or these sheet materials, deposit the layer that at least one deck forms primarily of the mixture of following component: (i) guarantees its painted and inorganic filler that is mechanical enhancer, and the crosslinkable polyorganosiloxane resin of (ii) at least one, described polyorganosiloxane resin does not contain or contains the precursor of carbonaceous material hardly, described filler (i) is distributed in described crosslinkable silicone resin.
13. methods as claimed in claim 12, is characterized in that, described deposition is undertaken by brushing deposition, blade coating deposition, sprayed deposit, electrostatic precipitation, immersion deposition, curtain deposition, serigraphy, deposits preferably by serigraphy.
14. methods as described in claim 12 or 13, it is characterized in that, described filler has layer structure at least partially.
15. methods according to any one of claim 12-14, it is characterized in that, the purity of the crosslinkable polyorganosiloxane resin of described at least one is at least 90 % by weight, is most preferably at least 95 % by weight.
16. methods according to any one of claim 12-15, it is characterized in that, the method also comprises:
The layer of described deposition or the layer of whole described deposition and precursor plate are heat-treated.
17. methods as claimed in claim 16, it is characterized in that, the precursor plate of described sheet material carries out described deposition, described heat treatment is carried out under certain conditions, this condition guarantees described precursor plate to be converted into described sheet material, and guarantees that crosslinked, fixing and pyrolysis occur the layer of described deposition.
18. methods as claimed in claim 16, it is characterized in that, glass-ceramic or glass plate carry out described deposition, and described heat treatment is carried out under certain conditions, this condition guarantees the crosslinked of the layer making described deposition, and guarantees this crosslinked layer is fixed on described sheet material.
19. methods as claimed in claim 16, it is characterized in that, glass-ceramic or glass plate carry out described deposition, described heat treatment is carried out under certain conditions, this condition guarantees the crosslinked of the layer making described deposition, and guarantee to make this crosslinked layer be fixed on described sheet material, also guarantee the pyrolysis of described layer.
20. methods as claimed in claim 16, it is characterized in that, glass-ceramic or glass plate carry out described deposition, to form mixed type coating, described heat treatment is: heat-treat first under certain conditions, this condition guarantees that the layer of described deposition is cross-linked, also guarantee that this crosslinked layer is fixed on described sheet material, then only heat-treat a part for described fixing cross-linked layer under certain condition, after described, the heat treated condition of a step guarantees described fixing crosslinked layer generation pyrolysis.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0403125A FR2868065B1 (en) | 2004-03-26 | 2004-03-26 | REINFORCING PLATES IN VITROCERAMIC OR GLASS; REINFORCED PLATES |
| FR0403123A FR2868066B1 (en) | 2004-03-26 | 2004-03-26 | VITROCERAMIC AND GLASS PLATES, HEATING PLATES, PREPARATION |
| FR04/03125 | 2004-03-26 | ||
| FR04/03123 | 2004-03-26 | ||
| US63504704P | 2004-12-09 | 2004-12-09 | |
| US60/635,047 | 2004-12-09 | ||
| US63495704P | 2004-12-10 | 2004-12-10 | |
| US60/634,957 | 2004-12-10 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005800094351A Division CN1934045A (en) | 2004-03-26 | 2005-03-23 | Glass-ceramic and glass plates and heating plates and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104691056A true CN104691056A (en) | 2015-06-10 |
Family
ID=53338790
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510058469.5A Pending CN104691056A (en) | 2004-03-26 | 2005-03-23 | Glass-ceramic and glass plates and heating plates and its manufacture |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN104691056A (en) |
| ES (1) | ES2707200T3 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110382428A (en) * | 2017-03-13 | 2019-10-25 | 尤罗科拉公司 | The glass and ceramic product shown with light |
| CN113165962A (en) * | 2018-12-20 | 2021-07-23 | 尤罗科拉公司 | Glass-ceramic article |
| CN113165963A (en) * | 2018-12-20 | 2021-07-23 | 尤罗科拉公司 | Glass-ceramic article |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3622754A (en) * | 1970-07-24 | 1971-11-23 | Gen Electric | Glass plate surface heating unit with even temperature distribution |
| JP2001233636A (en) * | 2000-02-23 | 2001-08-28 | Narumi China Corp | Glass ceramic with pearl-like muffle painting and method for producing the same |
| CN1357296A (en) * | 2000-11-11 | 2002-07-10 | 肖特玻璃制造厂 | Cooker |
-
2005
- 2005-03-23 CN CN201510058469.5A patent/CN104691056A/en active Pending
- 2005-03-23 ES ES05716427T patent/ES2707200T3/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3622754A (en) * | 1970-07-24 | 1971-11-23 | Gen Electric | Glass plate surface heating unit with even temperature distribution |
| JP2001233636A (en) * | 2000-02-23 | 2001-08-28 | Narumi China Corp | Glass ceramic with pearl-like muffle painting and method for producing the same |
| CN1357296A (en) * | 2000-11-11 | 2002-07-10 | 肖特玻璃制造厂 | Cooker |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110382428A (en) * | 2017-03-13 | 2019-10-25 | 尤罗科拉公司 | The glass and ceramic product shown with light |
| CN113165962A (en) * | 2018-12-20 | 2021-07-23 | 尤罗科拉公司 | Glass-ceramic article |
| CN113165963A (en) * | 2018-12-20 | 2021-07-23 | 尤罗科拉公司 | Glass-ceramic article |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2707200T3 (en) | 2019-04-02 |
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