CN105585892B - Golden clothes decorative composition and its manufacturing method with selected metal composition - Google Patents
Golden clothes decorative composition and its manufacturing method with selected metal composition Download PDFInfo
- Publication number
- CN105585892B CN105585892B CN201510764654.6A CN201510764654A CN105585892B CN 105585892 B CN105585892 B CN 105585892B CN 201510764654 A CN201510764654 A CN 201510764654A CN 105585892 B CN105585892 B CN 105585892B
- Authority
- CN
- China
- Prior art keywords
- composition
- layer
- weight
- metal
- carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
- B44C1/175—Transfer using solvent
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
- C04B41/5116—Ag or Au
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/88—Metals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00965—Uses not provided for elsewhere in C04B2111/00 for household applications, e.g. use of materials as cooking ware
Abstract
The present invention relates to the golden clothes decorative composition formed with selected metal and its manufacturing methods.In particular it relates to which a kind of composition, includes i. organic carrier as component；Ii. if applicable, inorganic additive；It iii. include the metal organic compound of metallic gold (Au), aluminium (Al), tin (Sn) and bismuth (Bi)；Wherein the ratio of Bi:Sn is in the range of 10:1 to 50:1；And the ratio of Al:Sn is in the range of 1:1 to 15:1.The invention further relates to a kind of layer structure, the precursor of layer structure and a kind of methods for manufacturing layer structure.
Description
Technical field
The present invention relates to a kind of compositions, include i. organic carrier as component；If applicable, inorganic additive；Packet
Containing metallic gold (Au), aluminium (Al), tin (Sn) and bismuth (Bi) metal organic compound；Wherein the ratio of Bi:Sn 10:1 extremely
In the range of 50:1；And the ratio of Al:Sn is in the range of 1:1 to 15:1.The invention further relates to a kind of layer structures comprising
I. with the substrate on surface, the metal layer that ii. is at least partly superimposed on said surface and is joined on the surface；Wherein
The metal layer includes metallic gold (Au), aluminium (Al), tin (Sn) and bismuth (Bi)；And wherein in the metal layer Bi:Sn ratio
In the range of 10:1 to 50:1；And the ratio of Al:Sn is in the range of 1:1 to 15:1.The invention further relates to before layer structure
Body comprising a) with the substrate on surface, b) at least partly it is superimposed composition on said surface；The wherein composition
Including comprising metallic gold (Au), aluminium (Al), tin (Sn) and bismuth (Bi) metal organic compound；And wherein in the composition
The ratio of Bi:Sn is in the range of 10:1 to 50:1；And the ratio of Al:Sn is in the range of 1:1 to 15:1.The invention further relates to
A method of manufacture layer structure comprising step: S1. provides the substrate with surface；S2. the surface at least
It is superimposed first chamber in a part, while obtaining the precursor of layered structure；S3. the precursor of layered structure is applied
With at least 500 DEG C at a temperature of processing.
Background technique
Various fields are used for containing metal composites.Correspondingly, such as 3481758 A, US 2008/03364 of patent application US
Described in 2013/011957 A1 of A1 and US, it is usually used in manufacturing semiconductor element containing metal composites.It is also used containing metal composites
Make the decoration of various objects.Usually using decorating objects containing metal composites to realize special-effect.Such as in patent application DE
The various compositions with different metal composition are described in 197 04 479 A1.
The document of reference none be related to being adapted to provide for showing well decorating property and good resistance to microwave coating containing gold
Belong to composition, the also referred to as selection of flash of light material (luster).
Summary of the invention
In general, it is an object of the invention at least partly overcome the shortcomings that generating according to the prior art.
Another object is to provide the composition for being suitable for forming durable film.
A further object be to provide suitable for formed durable film (such as on object dish-washing machine and micro-wave oven it is durable
Ornament form) composition.
Another object is to provide cheap composition.
A further object is to provide can generate decorative, especially glossiness ornament on different objects
(decor) composition.
A further object, which is to provide, is suitable for being formed durable film (such as the decoration with low noble metal ratio on object
Object form) composition.
One purpose also resides in the composition for providing and can be inexpensive and easily processing.
Another object is shown as far as possible most when being to provide especially in dish-washing machine and micro-wave oven using the layer structure
The layer structure of high-durability.
In addition, one is designed to provide the method for manufacturing layer structure in a manner of inexpensive and timesaving.
Another object is to provide the method for manufacturing layer structure as stable as possible.
First theme of the invention helps to solve one of above-mentioned purpose.The first embodiment of the theme is
[1] a kind of composition includes as component
I. organic carrier；
Ii. if applicable, inorganic additive；
It iii. include the metal organic compound of metallic gold (Au), aluminium (Al), tin (Sn) and bismuth (Bi)；
Wherein
The ratio of-Bi:Sn is in the range of 10:1 to 50:1；And
The ratio of-Al:Sn is in the range of 1:1 to 15:1.
Preferably, composition of the invention is very suitable to be applied on object, such as substrate preferably after the heating in institute
It states and forms securely durable ornament on object.The composition may include those skilled in the art thus purposes selection any group
Point.The composition is preferably liquid or paste.Apply liquid composition preferably by brush, by spraying or by dipping.It is excellent
Choosing applies paste composition by silk-screen printing, stencilization, bat printing or letterpress.But the composition can also be with powder shape
Formula exists.
It can be those skilled in the art according to the organic carrier of component i and be used in any organic of composition of the invention
Carrier.It is different from the component i. and iii. of the composition according to the inorganic additive of component ii.Carrier, nothing is described more fully below
The property and preferred embodiment of machine additive and metal organic compound.
In a preferred embodiment preferably as the composition existing for non-viscous liquid, the composition includes extremely
Few one kind, preferably at least two kinds or preferred all following properties:
A1. at least 30 weight % of the total weight of the composition, preferably at least 35 weight % or preferably at least 40 weight %'s
Solvent content.
A2. 5 to 30 weight %'s of the total weight of the composition, preferably 8 to 25 weight % or preferably 10 to 20 weight % is viscous
Mixture content.
A3. 1:100 to 100:1, preferably 1:50 to 50:1, the proton solvent of particularly preferred 1:5 to 5:1 with it is non-proton molten
The ratio of agent.
A4. 1 to 500 mPa*s, the preferably viscosity of 2 to 450 mPa*s or preferably 5 to 400 mPa*s.
The composition further preferably includes at least property a4.
In another preferred embodiment of the composition of preferably paste, the composition includes at least one, preferably
At least two or preferably all following properties:
B1. at least 1 weight % of the total weight of the composition, the preferably at least solvent of 3 weight % or preferably at least 5 weight %
Content, wherein the solid content of preferably more than 60 weight %.
B2. 5 to 95 weight %'s of the total weight of the composition, preferably 7 to 90 weight % or preferably 10 to 50 weight % is viscous
Mixture content.
B3. 1:100 to 100:1, preferably 1:50 to 50:1, the proton solvent of particularly preferred 1:5 to 5:1 with it is non-proton molten
The ratio of agent.
B4. 500 to 50000 mPa*s's, preferably 700 to 45000 mPa*s or preferably 1000 to 40000 mPa*s is viscous
Degree.
The composition further preferably includes at least property b4.
Composition with property a1. to a4. is preferably very suitable to be applied to substrate with direct application method as described below
On.
Composition with property b1. to b4. is preferably very suitable to that (its is excellent with directly or indirectly application method as described below
Choosing is print process) it is applied in substrate.
The composition includes the preferred 20-95 weight % or preferably 25 to 90 weight % or preferably 30 of the total weight of the composition
To the organic carrier of 85 weight %.
The metal of the composition can be used as metal element presence, such as with powder, such as the form of bronze, or as metal-
Organic compound or as metal salt or metal oxide or as the form mixed form exist.Unless clearly making
Different regulations, the weight specification of the tenor of the composition simply mean to the weight fraction of the metal in the composition, nothing
Metal organic compound is still used as pure element by it or is added as salt or oxide.Do not consider to be bonded in this respect
The weight fraction of part on to the metal.This is also applied for the formation of the mutual ratio of certain metals.Similarly, only consider gold
The weight fraction of category and/or metal ion, the weight fraction without considering ligand.
According to the present invention, bismuth (Bi): the ratio of tin (Sn) is in the range of 10:1 to 50:1 or preferably in 15:1 to 40:1
In the range of or preferably in the range of 20:1 to 30:1.The composition preferably includes the 0.02 to 3 of the total weight of the composition
The tin of weight % or preferably 0.04 to 2.0 weight % or preferably 0.07 to 1.5 weight %.
Similarly, according to the present invention, aluminium (Al): the ratio of tin (Sn) is in the range of 1:1 to 15:1 or preferably in 1.1:1
In the range of to 10:1 or preferably in the range of 1.1:1 to 8:1.
The composition preferably includes 0.1 to 40 weight % of the total weight of the composition, preferably 0.5 to 30 weight % or excellent
Select the gold of 1 to 20 weight %.Golden and non-noble metal ratio is it is also preferred that in the range of 1:1 to 6:1 or preferably in 1.4:1 to 5:
In the range of 1 or preferably in the range of 1.6:1 to 4.5:1.Noble metal and non-noble metal ratio are it is also preferred that in 1:1 to 8:1
In the range of or preferably in the range of 1.4:1 to 6:1 or preferably in the range of 1.6:1 to 5:1.Noble metal should be understood
It is all metals for belonging to the race selected from ruthenium, rhodium, palladium, silver, osmium, iridium, platinum and gold.Base metal should be construed as being not belonging to select
From all metals of the race of ruthenium, rhodium, palladium, silver, osmium, iridium, platinum and gold.
The summation of all components of the composition adds up to 100 weight % always.
[2] according to the composition of embodiment 1, wherein the composition includes the 0.03 of the total weight of the composition
To the aluminium of 10 weight % or preferably 0.04 to 5 weight % or preferably 0.05 to 2 weight %.
Aluminium in the composition can be used as metal element or metal organic compound or also as metal salt or at least
The mixed form of two kinds of forms exists.
[3] according to the composition of any one of embodiment 1 or 2, wherein the composition includes the total of the composition
0.05 to 15 weight % of weight or the bismuth of preferably 0.1 to 10 weight % or preferably 0.2 to 8 weight %.
Bismuth in the composition can be used as metal element or metal organic compound or also as metal salt or at least
The mixed form of two kinds of forms exists.
[4] according to the composition of any one of embodiment 1 to 3, wherein the composition includes the total of the composition
Weight is less than 5 weight % platinum or preferably less than 4 weight % platinum or preferably less than 3 weight % platinum or preferably less than 2 weight % platinum, and institute
State in composition the weight ratio of gold and the weight summation of all other metal in the range of 1:1 to 6:1 or preferably 1.5:1 extremely
In the range of 5:1 or preferably in the range of 2:1 to 4:1.
The composition preferably include the total weight of the composition 0 to 5 weight % or preferably 0.05 to 4 weight % or
It is preferred that the platinum of 0.1 to 3 weight %.Platinum in the composition can be used as metal element or metal organic compound or also conduct
Metal salt or metal oxide or at least two mixed form in the form of described four kinds exist.
The composition preferably includes palladium.The composition preferably include the total weight of the composition less than 1 weight %
Or preferably less than 0.9 weight % or preferably less than 0.8 weight % palladium.The composition preferably includes the total weight of the composition
The palladium of 0.01 to 1 weight % or preferably 0.05 to 0.9 weight % or preferably 0.1 to 0.8 weight %.Palladium in the composition can
As metal element or metal organic compound or also as metal salt or metal oxide or in the form of at least two is described
Mixed form exists.
[5] according to the composition of any one of embodiment 1 to 4, wherein Ni content is the total weight of the composition
Less than 0.05 weight % or preferably smaller than 0.03 weight % or preferably smaller than 0.01 weight %.
The composition preferably include 0.001 to the 0.1 weight % or preferably 0.001 of the total weight of the composition to
The nickel of 0.05 weight % or preferably 0.001 to 0.01 weight %.In addition, the composition is not preferably nickeliferous.
[6] according to the composition of any one of embodiment 1 to 5, wherein model of the ratio of Bi:Sn in 11:1 to 47:1
In enclosing or preferably in the range of 13:1 to 46:1 or preferably in the range of 15:1 to 45:1.
[7] according to the composition of any one of embodiment 1 to 3, wherein model of the ratio of Al:Sn in 1.1:1 to 15:1
In enclosing or preferably in the range of 2:1 to 13:1 or preferably in the range of 2.5:1 to 11:1.
[8] according to the composition of any one of embodiment 1 to 3, wherein the metal organic compound further wraps
Include selected from platinum (Pt), palladium (Pd), rhodium (Rh), indium (In), silicon (Si), zirconium (Zr), osmium (Os), chromium (Cr), titanium (Ti) metal or
Wherein at least two kinds of combination.
Metal stated hereinabove is also referred to as the additional metal of the composition.The additional metal can be used as additional gold
Category-organic compound exists as oxide, as the mixture of salt, element or above-mentioned form.Unless otherwise prescribed, about
The following weight specification of the additional metal simply means to the tenor of the additional metal, even if the additional metal is as gold
Category-organic compound, oxide, salt or other compounds exist.The composition preferably includes the total weight of the composition
0.01 to 10 weight % or preferably 0.05 to 5 weight % or preferably 0.07 to 4 weight % the additional metal.The combination
Object preferably includes 0 to the 1 weight % or preferably 0.1 to 0.7 weight % or preferably 0.2 to 0.5 weight of the total weight of the composition
Measure the palladium of %.The composition preferably includes 0 to the 0.5 weight % or preferably 0.1 to 0.4 weight % of the total weight of the composition
Or the indium of preferably 0.1 to 0.3 weight %.The composition preferably include the total weight of the composition 0.01 to 2 weight % or
It is preferred that the silicon of 0.05 to 1 weight % or preferably 0.1 to 0.7 weight %.The composition preferably includes the gross weight of the composition
0.01 to 2 weight % of amount or the zirconium of preferably 0.02 to 1 weight % or preferably 0.03 to 0.7 weight %.The composition preferably wraps
Include 0 to the 1 weight % or preferably 0.02 to 0.8 weight % or preferably 0.03 to 0.5 weight % of the total weight of the composition
Osmium.The composition preferably includes 0 to the 1 weight % or preferably 0.02 to 0.8 weight % or excellent of the total weight of the composition
Select the chromium of 0.03 to 0.5 weight %.The composition preferably includes 0 to the 1 weight % or preferred of the total weight of the composition
The titanium of 0.02 to 0.8 weight % or preferably 0.03 to 0.5 weight %.
[9] according to the composition of any one of embodiment 1 to 8, wherein the metal organic compound has unit
Be selected from alcoholates and oxalate/ester, ester, carboxylate radical/ester, halogenated carboxylic acid root/ester, hydroxycarboxylic acid root/ester, acetone acid group/ester,
Ketone acid root/ester, phosphate, orthophosphite/ester, phosphide, phosphine, sulfonate radical/ester, mercaptide (thiolate), sulphur
Alcohol, amine, amide and thio resin acid group/ester (sulforesinate) or in which at least two mixture.
The organic component of the metal organic compound is preferably mercaptan or carboxylic acid, especially thylhexoic acid.If described
Metal is selected from noble metal, and the organic component is preferably mercaptan.Preferably, described to have if the metal is selected from base metal
Machine component is carboxylic acid, such as thylhexoic acid.
[10] according to the composition of any one of embodiment 1 to 9, wherein the inorganic additive is selected from oxide, hydrogen
Oxide, nitrate, carbonate, sulfide, halide, sulfate, thiosulfate or in which at least two mixture.Institute
State the mixture that inorganic additive is preferably selected from talcum, pearlescent pigment and kaolin or in which at least two.
[11] according to the composition of any one of embodiment 1 to 10, wherein the organic carrier be selected from organic solvent,
Or mixtures thereof organic bond.
The organic solvent is preferably selected from terpenes, alicyclic or aromatic hydrocarbon, ketone, ester, alcohol, for example, ethyl alcohol, isopropanol or oneself
Alcohol or in which at least two mixture.The solvent is preferably one of above-mentioned solvent.
The organic bond can be any adhesive that those skilled in the art are used in this purposes.It is described organic viscous
Mixture is preferably selected from the adhesive as described in organic carrier.
[12] according to the composition of any one of embodiment 1 to 11, wherein the metal organic compound includes rhodium
(Rh)。
The composition preferably include 0.001 to the 0.1 weight % or preferably 0.001 of the total weight of the composition to
The rhodium of 0.02 weight % or preferably 0.001 to 0.4 weight %.
Another theme of the invention is a kind of layer structure.The basis of layered structure is stated in following embodiment
The first design of the invention:
[13] a kind of layer structure comprising
I) with the substrate on surface
Ii the metal layer for) being at least partly superimposed on said surface and being joined on the surface；
Wherein the metal layer includes metallic gold (Au), aluminium (Al), tin (Sn) and bismuth (Bi), and wherein in the metal layer
In,
The ratio of-Bi:Sn is in the range of 10:1 to 50:1；And
The ratio of-Al:Sn is in the range of 1:1 to 15:1.
Layered structure can have any shape.Layered structure preferably has selected from circle, waveform, cylinder
Shape, cuboid, rectangle, cone, tubular, cone-shaped shape or in which at least two combination.The substrate may include this
Field technical staff is used in any material of this purposes.The substrate preferably has the surface that can apply metal layer.Below more in detail
Thin description substrate and its property.The method of the invention being described below is preferred for applying metal layer.Composition of the invention
It is preferably used as the coating for this purposes.Above for all features and component as defined in composition of the invention and these groups
Split-phase is preferably also applied for the metal layer for mutual relative ratios.
[14] according to the layer structure of embodiment 13, wherein the substrate is selected from glass, ceramics, porcelain, ceramic tile, gold
Belong to, polymer or in which at least two combination, wherein glass and ceramics are preferred.
Another theme of the invention is related to a kind of precursor.The precursor is stated in following embodiment according to the present invention
The first design:
[15] precursor of layer structure comprising
A) with the substrate on surface；
B) composition in superposition at least a portion of the surface；
Wherein the composition include comprising metallic gold (Au), aluminium (Al), tin (Sn) and bismuth (Bi) metal-organic compound
Object；And
Wherein, in the composition,
The ratio of-Bi:Sn is in the range of 10:1 to 50:1；And
The ratio of-Al:Sn is in the range of 1:1 to 15:1.
The precursor of layered structure can be those skilled in the art can thus purposes selection any precursor.Substrate
Feature is apparent from subsequent description and the description of layer structure and the description of composition and also should apply to precursor.It closes
In the composition is applied directly to the method in substrate, with reference to the method for manufacture layer structure of the invention.
B) partial stack of composition described in item on the surface of the substrate can be directly or indirectly is folded by the composition
Add.Directly superposition can be realized such as silk-screen printing, bat printing and by ink jet printing or spray coating method for example by print process.It closes
In the composition is applied directly to the various methods in substrate, with reference to the method for manufacture layer structure of the invention.Indirectly
Superposition preferably applies the composition by the carrier structure by the decal paper form comprising the composition and carries out.Below more
The carrier structure of the decal paper is discussed in detail.
[16] according to the precursor of embodiment 15, further comprising:
C) carrier layer；With
At least one following layers
D) layer that can be melted in the range of 40 to 80 DEG C；
E) inorganic layer；
F) water not soluble layer.
The embodiment 16 of the precursor also includes at least one carrier layer in addition to the substrate and the composition.It is described
Carrier layer may include that the composition is carried before being highly suitable for applying the composition in substrate is described without making
Composition scatter, shift, oozing out or change in any other way its structure arrangement any material.The carrier layer is preferably wrapped
Include Paper or cardboard.The carrier layer preferably includes 50 to the 100 weight % or preferably 70 to 100 weights of the total weight of carrier structure
Measure the Paper or cardboard of % or preferably 90 to 100 weight %.The carrier structure preferably has 0.5 micron to 2 millimeters, preferably 1 micron
To 1.5 millimeters or preferably 2 microns to 1 millimeter of thickness.The carrier structure preferably have 1 to 1,000 centimetre or preferably 5 to
500 centimetres or preferably 10 to 200 centimetres of length.Described device preferably have 1 to 1,000 centimetre or preferably 5 to 500 centimetres or
It is preferred that 10 to 200 centimetres of width.The carrier layer preferably has 10 square centimeters to 100 square metres or preferably 20 square centimeters
To 50 square metres or preferably 30 square centimeters to 10 square metres of the surface area formed by length and width.
The precursor preferably comprises extra play.Precursor in embodiment 16 preferably comprises can be in the range of 40 to 80 DEG C
First extra play of the layer d) form of melting simultaneously should hereinafter be referred to as meltable layer.Meltable layer d) is for keeping the carrier layer easy
It is separated with the composition, therefore it is hereinafter also referred to as fusible separating layer.If meltable layer d) is heated to above institute
The fusing point of meltable layer is stated, the separating layer is easy to remove from the composition.
In a preferred embodiment of the precursor, the precursor from embodiment 16 includes straight with the composition
The meltable layer d) of contact.It is preferred that meltable layer d) is arranged between carrier layer and composition.
Meltable layer d) from embodiment 16 preferably includes to be very suitable to and heating in the range of 40 to 80 DEG C
The material of melting.The material that can be melted between 40 to 80 DEG C is preferably wax, waxy material or waxy material.The wax preferably selects
Freely above to wax as defined in adhesive.Wax, paraffin are preferred.
Embodiment 16 preferably includes at least one second extra play.It is insoluble that second extra play can be selected from inorganic layer e), water
The combination of layer f) or both.
Inorganic layer e) can be used for stablizing and protecting the composition.Inorganic layer e) is preferably selected from glass, glass frit
(glass frit), ceramics or combinations thereof.Glass and ceramics can be to those of substrate description.
Soluble layer f) is not mainly used for stablizing the composition before the composition is transferred in substrate water.Water is insoluble
Layer f) preferably includes seal coat.The seal coat is preferably translucent in the visible-range of wavelength.The seal coat
Be preferably selected from acrylic acid seal coat, methacrylic resin, as polyacrylate or polymethacrylate polymer or its
In at least two mixture.
In a preferred embodiment of the precursor of embodiment 16, preferably there is meltable layer d) afterwards in carrier layer c),
Followed by composition b).It is preferred that there is water not soluble layer f) afterwards in composition b).In another preferred embodiment of the precursor
In, the inorganic layer e) of glass frit form is set between meltable layer d) and water not soluble layer f).Alternatively or in addition, inorganic layer e) is also
It can connect after water not soluble layer f).In another alternate embodiment of the precursor, in addition to the first inorganic layer e) or substitution first
The second inorganic layer e) is arranged in inorganic layer e) between meltable layer d) and composition b).
Another theme of the invention is related to a kind of carrier structure.The root of the carrier structure is stated in following embodiment
According to the first design of the invention:
[17] a kind of carrier structure comprising
I. carrier layer；
II. extra play, wherein the extra play is fusing point water-soluble or with 40 to 80 DEG C；
III. a kind of composition includes as component
I1. organic carrier；
I2. if applicable, inorganic additive；
It i3. include the metal organic compound of metallic gold (Au), aluminium (Al), tin (Sn) and bismuth (Bi)；Wherein
The ratio of-Bi:Sn is in the range of 10:1 to 50:1；And
The ratio of-Al:Sn is in the range of 1:1 to 15:1.
The carrier structure is for being transferred to substrate for composition of the invention as known in decal paper form.
The carrier layer may include any material.The carrier layer carries before being highly suitable for applying the composition in substrate
The composition is without making the composition scatter, shifting, ooze out or change in any other way its structure arrangement.For
This, the carrier structure can be easy the release load comprising various layers after the composition is being transferred in substrate
Body.About the composition and design of the carrier layer, the feature of the carrier layer in precursor in reference implementation scheme 16.
The extra play can be water-soluble layer or the above meltable layer of the type described in the precursor in embodiment 16
d).The extra play has 0.5 to 200 micron, preferably 1 to 100 micron or preferably 10 to 50 microns of thickness.According to described attached
Adding layer is water-soluble layer or meltable layer, and the design of the carrier structure can be different.
In a preferred embodiment of the carrier structure, the carrier structure includes water-soluble layer.The water-soluble layer
Preferably include the material for being very suitable to be dissolved in water.The water-soluble layer is preferably selected from salt, carbohydrate, such as sugar, class sugar object
Matter or in which at least two combination.The salt is preferably selected from salt water (NaCl), potassium chloride (KCl), lithium chloride (LiCl), magnesium chloride
(MgCl2) or in which at least two mixture.The sugar or class sugar substance be preferably selected from glucose, fructose, saccharin, maltose,
Dextrin, maltodextrin, gum arabic or in which at least two mixture.
In another preferred embodiment of the present, the carrier structure includes the layer d) of the fusing point with 40 to 80 DEG C as additional
Layer.About the feature and material of layer d), the feature and material of the layer d) in reference implementation scheme 16.
[18] further comprise at least one following extra play according to the carrier structure of embodiment 17:
E) inorganic layer；
F) water not soluble layer.
If the carrier structure includes water-soluble layer as extra play, the extra play is connect on side in carrier layer
Afterwards, and the composition connects after the extra play.Second extra play may be alternatively located between the water-soluble layer and the composition.
Second extra play is preferably the inorganic layer e) of the type to the precursor description in embodiment 16 above.Feature and material can be with
The inorganic layer e) of embodiment 16 is described identical.Inorganic layer e) preferably comprises particle.The inorganic layer is preferably comprised to be stood often
Particle in square centimetre of 10 to 1,000 particle ranges.The inorganic layer is preferably glassy layer or glass frit.
It is further preferred that the carrier structure further includes water after the composition not soluble layer f).Soluble layer f) is not suitable for water
In the layer f) from embodiment 16, compositions and features also should apply to this.
The composition is preferably applied on extra play with pattern form, such as by silk-screen printing.It is preferred that passing through silk screen
Printing by water not soluble layer and if there is inorganic layer be applied on the composition.It can soluble layer be applied to the load by water
In the different zones of body structure.In a preferred embodiment of the carrier structure, by water not soluble layer and if there is
Inorganic layer is applied on region identical with the composition.In another embodiment, by water not soluble layer and if there is
Inorganic layer be applied in the whole surface of the carrier structure.
If the carrier structure includes that meltable layer d) is used as extra play, a preferred embodiment of the carrier structure
There is meltable layer d) first, then in the followed by described composition of carrier layer.In another preferred implementation side of the carrier structure
In case, above as described in the carrier structure with water-soluble layer, the second extra play be located at meltable layer d) and the composition b) it
Between.Second extra play is preferably glass frit.
Another theme of the invention is related to the method for manufacturing layer structure.The method is stated in following embodiment
The first implementation according to the present invention:
[19] method of layer structure is manufactured comprising step:
S1., the substrate for having surface is provided；
S2. it is superimposed first chamber at least a portion of the surface, while before obtaining layered structure
Body；
S3. to the precursor of layered structure impose at least 500 DEG C at a temperature of processing.
The substrate, the composition, the precursor and layered structure feature from being provided for these objects
It is apparent and also should apply to the method in information.
S1. the offer of substrate
Substrate in step S1. provide can by those skilled in the art can purposes design thus it is any in a manner of into
Row.It is preferred that suitably providing substrate so that substrate surface is easy that the composition is allowed to be added to thereon.Based on the gross area of substrate,
The superposition is preferably directed to 1 to 100 % or preferably 5 to 90 % or preferably 10 to 80 % of substrate.
S2. it is superimposed the composition
Superposition in step S2. can be those skilled in the art can thus purposes selection any superposition.The superposition can
To be any kind of application or deposition.The superposition carries out preferably in the form of the method that the composition is applied in substrate.
Applying method (superposition) described below is the different modes for the composition being applied or being deposited in substrate.
In additive process, the composition is at least partly added on substrate surface, wherein it is preferred that applying described group
Close object.The superposition or apply preferably can be the combination for applying the composition or being impregnated into the composition or both.It is logical
Cross deposit the composition and apply can for example by spin coating, immersion, curtain coating, dropwise addition, sputtering, spraying, with scraper plate apply, on
Paint or printing (such as by metering pump) pass through ink printing, silk-screen printing, intaglio printing, hectographic printing or bat printing to substrate
It is realized on layer.It is applied the composition on substrate surface preferably by metering pump, silk-screen printing or intaglio printing.It is preferred that
Ground preferably applies composition with 0.5 micron to 250 microns of wet-film thickness with 2 microns to 50 microns of wet-film thickness.
Within the scope of the invention, deposition is understood to refer to by auxiliary tool, such as printer nozzle or silk screen
The composition for being used to deposit (it is preferably also referred to as printing material) is applied to the surface to be superimposed by the silk screen of printing equipment.
This can be carried out by different auxiliary tools.Correspondingly, the printing material for applying or being superimposed can pass through slotted nozzle
(slitted nozzle) spraying is sputtered or is deposited on substrate surface.Noticeable other methods include curtain coating and spin coating.
Alternatively or in addition, the printing material for applying or being superimposed for example can apply and/or be printed onto substrate table by roller or roller
On face.Micro- metering or ink jet printing through nozzle are for example referred to as spraying and/or sputtering method.It in this respect, can be to for applying
The printing material for adding or being superimposed applies pressure or the printing material for being used to apply simply is instilled into surface via nozzle is applied.
It is preferable to use silk screen print methods or gravure printing method as printing process.In silk screen print method, what is be superimposed
Above substrate in object, such as this situation placement have selected mesh size by form-stable material, such as wool, gold
Belong to, preferred steel, the silk screen that ceramic material or plastics are constituted.The printing material for being used to apply or be superimposed is applied to the silk screen
And sieve pore is pressed through using scraper plate.Since silk screen has pattern, can apply in the different location in silk screen different amounts of for applying
The printing material for adding or being superimposed.Correspondingly, the geometry of sieve pore and arrangement can be used for applying the uniform of the printing material for superposition
Film is alternate completely or nearly without being used for the region of the printing material of application and with the printing material for being largely used to apply
The region of material.Preferably, the uniform film for the printing material for being used to be superimposed is transferred to the surface.Silk screen sieve pore can also be with
It is partially enclosed by corresponding admixture (duplicating layer, screen printing template), so that printing material only has open sieve pore
It is transferred in substrate in limited area, for example to obtain limiting structure, such as pattern whereby.In addition, having and delimiting out instead of silk screen
The film (template) of aperture can also be used for being superimposed the printing material.Alternatively, transfer printing can be used, provides and for example print material
Transitional surface is expected, by the structuring printing material coining or roller coating that are used to be superimposed on the surface to be coated with.
The viscosity and polarity of printing material according to the design of nozzle and/or roller or roller and for its superposition, can be with
Apply the different layer of thickness on the required surface of substrate.Preferably, the layer applied in application or additive process have 0.5 to
100 microns, preferably 1 to 50 micron, particularly preferred 2 to 30 microns of thickness.The thickness of the layer applied during application is under
Wen Zhongying is referred to as wet layer thickness.Wet layer thickness depends on the material applied in additive process.It is surveyed immediately after being superimposed step
Measure wet layer thickness.
Dipping includes that surface to be coated is for example pulled through to the bath for being used for the printing material applied.Alternatively, as in dip-coating
Way is such, which can be simply dipped into the printing material for being used for applying and be pulled out again.Dipping can apply repeatedly
The different coating of thickness is obtained in journey.In addition, as above it was mentioned that the invention that coating layer thickness depends on the choosing of the printing material for application
It selects.Whereby, it can obtain with 0.5 to 100 micron, preferably 1 to 50 micron, particularly preferred 2 to 30 microns of wet layer thickness
Respective coatings.Also the combination of deposition and infusion process can be implemented.
In one embodiment, via the application aperture provided above the respective surfaces for the layer to be superimposed
(application opening) applies the printing material for application.Therefore, the application aperture is preferably by for application
Printing material is joined on the surface.One special feature of the method for also referred to as micro- metering (micro-dosing)
It is, is easy in object, the superposition coating as applied various thickness on the substrate surface in this situation.The application aperture can be in
What incumbent shape and size.This can be related to the application of the shape for example selected from round, oval, angular and star or combinations thereof
Aperture.The application aperture can have 10 nanometers to 1 millimeter, preferably 100 nanometers to 0.5 millimeter, and particularly preferred 100 nanometers to 100
The surface area of micron.Preferably, by 2,000 to 10,000 millibar, preferably 2,500 to 5,000 millibar, particularly preferred 3,000
The printing material for being used to apply is applied to surface through nozzle to 4,000 millibars of pressure.The printing material that will be used to be superimposed
Being joined on the surface for the equivalent layer to be superimposed can prevent the printing material for application from dripping (tearing from surface
Off).It may be implemented to apply highly uniform film on the surface whereby.
The application is carried out preferably by silk screen print method or gravure printing method.In gravure printing method, the application preferably from
Reel-to-reel (roll-to-roll) carries out.In a preferred refinement scheme of this method, in printing process via silk screen or
Pressure measuring cylinder applies printing material.The silk screen preferably includes the frame made of steel or stainless steel.Preferably, it is arranged in the frame
Grid or silk screen (the frame as a grid or screen arranged in it that) it is also preferred that by stainless steel
Silk or high strength synthetic fibre are constituted.
In a preferred refinement scheme of this method, which has 1 to 300 micron, preferably 2 to 200 microns or excellent
Select 3 to 90 microns of sieve pore width.This is respectively equivalent to about 70 to 635 mesh, about 100 to 500 mesh and about 200 to 400
Purpose sieve pore width, wherein mesh is equivalent to the unit of the mesh wire number of per inch and/or 2.54 centimetres of mesh wire number.About borrowing
Any commercially available scraper plate can be used as scraper plate in the application for helping silk-screen printing.The scraper plate preferably includes plastics.The scraper plate preferably has
There is the Squeegee hardness of 40 to 80 Shore As.The printing material preferably has 500 to 50,000 mPa*s or preferably 1,000 to 20000
The viscosity of mPa*s.
Layered structure is obtained after the composition is superimposed upon at least part surface of substrate in step S2.
Precursor.
S3. it handles at elevated temperatures
In step S3., the precursor is imposed at least 500 DEG C, preferably at least 600 DEG C or preferably at least 800 DEG C
At a temperature of processing.Processing at elevated temperatures, is also referred to as heat-treated, can purposes thus with those skilled in the art
Any mode of selection carries out.The heat treatment can be carried out for example by using radiation or convection current.Preferred heat treatment method packet
It includes infra-red radiation, flash illumination, hot-air or is handled in drying box or furnace.Hot place is carried out preferably by hot-air or in furnace
Reason.The heat treatment preferably includes heating period, holding stage and cooling stage.The duration of heating period is preferably 1 to 90
Minute, preferably 10 to 60 minutes, particularly preferred 15 to 50 minutes.The final temperature reached in the heating period is 600 to 1300
DEG C, preferably 700 to 900 DEG C, particularly preferred 750 to 850 DEG C.Kept for the duration in the holding stage of the final temperature preferred
It is 1 to 60 minute, preferably 2 to 30 minutes, particularly preferred 10 to 15 minutes.Cooling stage preferably carries out at room temperature.
[20] according to the method for embodiment 19, wherein the superposition in step S2. includes at least the following steps:
S4. any carrier structure according to aforementioned present invention is provided comprising with the fusible of 40 to 80 DEG C of fusing points
Layer；
S5. it is superimposed the carrier structure at least a portion of the surface, wherein the table of first chamber and substrate
Face directly contacts, while obtaining the precursor of layer structure；
S6. at least described meltable layer is heated to its melting temperature；
S7. carrier layer and meltable layer are removed from the precursor.
In this refinement scheme of the method, by carrier structure, (preferably the carrier structure of aforementioned present invention is upper
Decal paper form described in hereafter) it is applied in substrate.It can be with the phase Tongfang described in carrier structure of the invention above
Formula designs the substrate.In this refinement scheme of the method, the carrier structure includes the fusing point with 40 to 80 DEG C
Meltable layer；The function of meltable layer is appropriate connection carrier layer to allow to separate with the composition by the combination
Object stablizes the composition before being applied in substrate.Meltable layer is hereinafter also referred to as fusible separating layer.Meltable layer is preferred
Including as above as an alternative solution of carrier structure described in the wax with fusing point in the range.
Preferably, by simply by carrier structure pass through it includes the face of the composition be arranged on substrate surface come into
Superposition in row step S5..Therefore, the composition and the substrate are directly contacted in substrate surface.Directly contact should be managed
The composition and described in the case that solution is refers between the composition and the substrate without arranging any extra play
The direct contact of substrate.The placement can carry out under slightly elevated pressure.Preferably, it is described be placed in 1 to 20 kg or
It is preferred that being carried out under the pressure of 2 to 18 kg or preferably 3 to 15 kg.Can with those skilled in the art can thus purposes selection appoint
Where formula applies pressure.Preferably, the application of pressure includes placing weight, such as stamp.It in this respect can be with pattern form
Apply first chamber.The pattern delimited the 1:1 in carrier structure and as in decal paper in advance and shifted.
In step S6., will at least described meltable layer, the entire precursor being preferably made of substrate and carrier structure,
It is heated to the melting temperature of fusible separating layer.Can by those skilled in the art can thus purposes selection it is any in a manner of realize plus
Heat.Preferably, by furnace heat, by irradiation heating, geothermal liquid bath in heating, with hot gas heating or at least two
The combined method of these methods of kind realizes the heating in step 6..Heating can may be implemented in 40 to 80 DEG C of heating in furnace
Any of furnace in carry out.It can for example be carried out by infrared ray, ultraviolet light or combinations thereof by irradiation heating.In liquid
Heating can be carried out for example in a water bath in bath.It purposes can be selected thus by those skilled in the art with hot gas heating
It is any can heat gas, such as air, nitrogen or carbon dioxide carry out, and air is preferred.
Will be after at least described fusible separating layer be heated to its melting temperature in step S6., it can be in step S7. from institute
It states and removes carrier layer and fusible separating layer on precursor.In this case, first chamber stays in substrate.Further preferably by another
Additive composition is applied in first chamber or is applied to the substrate not yet contacted with first chamber by one carrier structure
On another surface.The method can be repeated as many times to apply the pattern of different pattern or different components being overlapped mutually
Onto substrate.
As described in step S3., the composition wherein applied can be imposed at least 500 DEG C, preferably together with substrate
Processing at a temperature of at least 800 DEG C or preferably at least 1,000 DEG C.Layer structure of the invention is obtained whereby.
[21] according to the method for embodiment 19, wherein the superposition in step S2. includes at least following additional step:
S8., any carrier structure according to aforementioned present invention including water-soluble layer is provided；
S9. carrier layer and water-soluble layer are removed from the composition；
S10. it is superimposed first chamber at least a portion of the surface, while obtaining the precursor of layer structure.
Also, it is preferred that this refinement scheme be to it is aforementioned it is according to the present invention manufacture layer structure method refinement side
The substitution of case.Firstly, providing the carrier structure of the invention with water-soluble layer (also referred to as water-soluble separating layer) in step s 8.
The carrier layer preferably includes Paper or cardboard.As described in carrier structure of the invention, which may include more above
The water-soluble substances of kind multiplicity.The water-soluble layer preferably includes dextrin.The water-soluble layer further preferably includes the 50 of the water-soluble layer total weight
To the dextrin of 100 weight % or preferably 70 to 100 weight % or preferably 90 to 100 weight %.
The carrier structure preferably also includes water not soluble layer.Soluble layer is not preferably seal coat to the water.The water not soluble layer, under
It is also referred to as seal coat in text, is preferably placed in carrier structure on that face backwards to carrier layer of the composition.
In step S9., carrier layer and water-soluble layer are removed from the composition together.In this case, covering applies
Layer prevents the composition to be disintegrated.It is preferred that removing carrier layer and separating layer by contacting at least described water-soluble layer with water.Also
It is preferred that by removing carrier layer and water-soluble layer all with water contact to realize.Since carrier layer is preferably made of paper, contact carrier
The water penetration carrier layer of layer simultaneously dissolves water-soluble layer.Therefore, the composition and seal coat are shelled with carrier layer and water-soluble layer together
From and expose the composition.Seal coat be preferably the composition provide it is enough support so that the composition, can
To shift substrate by being displaced (shifting) preferably by scraper plate or rubber wiper or other scrapers together with seal coat
On.The seal coat can undertake multi-functional in this respect.Firstly, it can be described group during being transferred in substrate
It closes object and bearing is provided.In addition, the seal coat can contain particle, such as glass frit, it is the layer after 500 DEG C or more processing
Shape structure provides scratch resistant protection.The layer structure can be protected from many external actions whereby, such as dish-washing machine detergent and microwave
Furnace.The seal coat can have with above to the identical composition of the seal coat of carrier structure description of the invention and property.Also
Additive composition is applied in first chamber or is applied to preferably by another carrier structure and is not yet connect with first chamber
On another surface of the substrate of touching.The method can be repeated as many times with being overlapped mutually different pattern or different components
Pattern be applied in substrate.It can also be with alternately applied the alternative carrier structure as described in the alternative in step S5
Different pattern.
As described in step S3., the composition wherein applied can be imposed at least 500 DEG C, preferably together with substrate
Processing at a temperature of at least 800 DEG C or preferably at least 1,000 DEG C.Layer structure of the invention is obtained whereby.
[22] according to the method for any one of embodiment 19,20 or 21, wherein the processing in step S3. is 500 to 1,
It is carried out at a temperature of 200 DEG C or preferably 600 to 1,100 DEG C or preferably 700 to 1,000 DEG C.
Carrier
The organic carrier is preferably liquid.The organic carrier can be by polarity organic carrier or nonpolar organic carrier
Or mixtures thereof constitute.
Preferably, at least part organic carrier is organic solvent.The organic solvent can be polar organic solvent or non-
Or mixtures thereof polar organic solvent.
In addition, the polar organic solvent can be polar protic organic solvent, polar non-proton organic solvent or its mixing
Object.The nonpolarity organic carrier is preferably non-polar organic solvent.
Preferably, which includes 2 to 20 or preferably 3 to 18 or preferably 4 to 15 carbon atoms.The pole
Property proton-organic solvent it is also preferred that comprising at least one polar protic residue, such as-OH ,-SH ,-NH ,-NH2,-COOH.Polarity matter
The representative instance of sub- organic solvent includes alcohol, amine (amine should be construed as aliphatic series and cycloaliphatic amines), amide and carboxylic acid.This is preferably
It is related to low-carbon alcohols, especially such as methanol, ethyl alcohol, 1- propyl alcohol, 2- propyl alcohol, n-butyl alcohol, 2- butanol, 2- methyl-1-propyl alcohol and 2- first
Base -2- propyl alcohol, preferably methanol, ethyl alcohol, propyl alcohol, butanol, methoxypropanol, ethyoxyl propyl alcohol, methyl cellosolve, ethyoxyl second
Alcohol, 4- methylol -1,3- dioxolanes or in which at least two mixture.In addition, the polar protic organic solvent can be selected from
Glycol, amine, amide and carboxylic acid or in which at least two mixture.The glycol can be selected from 1,2- ethylene glycol, 1,2- propylene glycol, 1,
2,3- glycerine (glycerol), 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, 2,3- butanediol, 1,2,3- butantriol, 1,
2- dihydroxy benzenes, 1,3- dihydroxy benzenes, 1,4- dihydroxy benzenes, 1,2,3- trihydroxy benzene, 1,2,4- trihydroxy benzene, 1,4- dihydroxy
Base -2,5- dinitrobenzene, L- adrenaline, monosaccharide, disaccharides, the monosaccharide in the mixture containing liquid polyol or disaccharides,
1,1,1- tri--(methylol) propane, pentaglycol 2-1,3, polyethylene glycol (preferably have 3 to 500 repetitions single
Member), such as mono- 1,2-PD, two -1,2-PDs, 1,2- butanediol, 2,3-butanediol or in which at least two mixing
Object.The amine can be selected from ammonia, methylamine, ethamine, n-propylamine, isopropylamine, n-butylamine, dimethylamine, diethylamine, two-n-propylamines, two-
N-butylamine, triethylamine, pyrrolidines, piperidines, piperazine, N- thyl-piperazin, n-ethylpiperazine, morpholine, ethylenediamine, 1,2- propane diamine,
1,3- propane diamine, two-(2- cyanoethyl) amine, two-(2- amino-ethyl) amine, three-(2- amino-ethyl)-amine, ethanol amine, diethanol
Amine, triethanolamine, Propanolamine, dipropanolamine and tripropanol amine or in which at least two mixture.The amide can be selected from formyl
Amine, acetamide, propionamide, butyramide, pentanamide, caproamide, heptamide, caprylamide or in which at least two mixture.It should
Carboxylic acid can be selected from formic acid, acetic acid, acrylic acid, oxalic acid, citric acid, benzoic acid, niacin, succinic acid, maleic acid, salicylic acid or in which
At least two mixture.The specified alcohol should be considered preferred.Preferably, the composition includes the total weight of the composition
The proton solvent of 5 to 35 weight % or preferably 8 to 30 weight % or preferably 15 to 27 weight %.
Outside polar proton-organic solvent, the composition further preferably includes at least one additional aprotic organic solvent.
The aprotic organic solvent can be selected from the mixture of ketone, aldehyde and sulfoxide or in which at least two.The ketone can be selected from ethylene carbonate,
N-Methyl pyrrolidone, N- ethyl pyrrolidone, cyclohexanone.The aldehyde can be selected from formaldehyde, acetaldehyde, propionic aldehyde, octanal or in which at least
Two kinds of mixture.The sulfoxide can be such as dimethyl sulfoxide.Preferably, the composition includes the 5 of the total weight of the composition
To the aprotic solvent of 35 weight % or preferably 10 to 30 weight % or preferably 15 to 27 weight %.
The organic carrier preferably includes adhesive as to the substituted or supplemented of the solvent.Further preferably at least another part
Organic carrier is adhesive.The adhesive can be used as proton organic carrier and exist as non-proton organic carrier.The adhesive
Usually there is the molecular weight higher than above-mentioned organic solvent.The adhesive further preferably has the viscosity higher than organic solvent.
Adhesive
The adhesive can be any adhesive that those skilled in the art can select for composition of the invention.The bonding
Agent is preferably selected from thermoplastic polymer, rigid plastics polymer (duroplastic polymer), resin and wax or in which at least
Two kinds of mixture.In this respect, these can be used alone or the adhesive of the adhesive as a variety of this kind of components mixes
Object uses.The thermoplastic polymer can be selected from acrylonitrile-butadiene-styrene (ABS), polyamide, polyaminoamide, poly-lactic acid ester, gather
Methyl methacrylate, polycarbonate, polyethylene terephthalate, polyethylene, polypropylene, polystyrene, polyether-ether-ketone
With polyvinyl chloride or in which at least two mixture.The rigid plastics polymer can be selected from melamine resin, epoxy resin,
Phenol resin, polyester resin or in which at least two mixture.The adhesive is preferably such as polyurethane, polyacrylate, gathers
Ester, polyvinyl alcohol, polysulfones or in which at least two mixture.
Resin
The resin is preferably selected from natural resin, sulfurised natural resins and such as vulcanizes dammar, pitch, rosin, rosin ester, pine
Fragrant modified resin, amino resins (respectively be preferably natural base), nitrocellulose, ketone resin, vulcanization terpene resin or in which
At least two mixture.
Wax
Wax is can to melt and Undec hydrocarbon compound at 40 DEG C or more.This preferably includes fatty alcohol, fatty acid amide, gathers
Olefin wax, ployalkylene glycol, polyester, paraffin, polyethylene and wherein at least two kinds of copolymer or mixture.
The adhesive is preferably selected from polyacrylic resin, polymethacrylate resin, polyvinylpyrrolidone, cellulose
Ether, such as hydroxyalkyl-, alkoxy-and carboxyl alkyl cellulose, polyamide, ployalkylene glycol such as polyethylene glycol, polyester, polyacrylamide
Amine, polyaminoamide, polyvinyl acetate, polyvinyl alcohol, alkyd resin, polyamine, polyurethane resin, hydrocarbon resin, urea-formaldehyde tree
Rouge, modified urea-formaldehyde resins, melamine resin, alkyd resin, polyurethane resin or epoxy resin or in which at least two
Mixture.
The composition preferably includes 5 to the 35 weight % or preferably 10 to 30 weight % or preferably 15 of the total weight of the composition
To the adhesive of 27 weight %.The composition further preferably includes 10 to the 30 weight % or preferably 13 to 25 of the total weight of the composition
The resin of weight % or preferably 15 to 23 weight %.
The organic carrier preferably comprises preferably in the range of 1:35 to 35:1 or preferably in the range of 1:20 to 20:1
Or the ratio of the proton solvent and aprotic solvent in the composition preferably in the range of 1:10 to 10:1.The composition is excellent
Choosing includes 10 to 40 weight % of the total weight of the composition or preferably the proton of 15 to 35 weight % or preferably 18 to 32 weight % carry
Body.The composition further preferably include the total weight of the composition 10 to 40 weight % or preferably 15 to 35 weight % or preferably 18 to
The non-proton carrier of 32 weight %.The composition preferably has the viscosity of 100 to 50,000 mPa*s.
Inorganic additive
The inorganic additive can be any inorganic additive that those skilled in the art are used in composition of the invention.
The inorganic additive is solid preferably at 20 DEG C.The inorganic additive is different from the component i. and iii. of the composition.It is inorganic
Additive is preferred for improving the wearability on surface and adjusts the obscure degree (dullness) and mechanical endurance on surface.As one
A option can add inorganic additive in the composition.The inorganic additive is preferably selected from glass, metal oxide, gold
Belong to hydroxide, metal nitrate, metal carbonate, metal sulfide, metal halide, metal sulfate, metal thiophosphate sulphur
Hydrochlorate, metal silicate, amine-oxides, ammonium hydroxide, ammonium nitrate, ammonium carbonate, ammonium sulfide, ammonium halide, ammonium sulfate, thiosulfuric acid
Ammonium, ammonium silicate, ceramics or in which at least two mixture.
The glass be preferably selected from alkali glass, alkali-free glass, silicate glass or in which at least two mixture.The glass
It is preferably selected from soda-lime glass, lead alkali glass, borosilicate glass, alumina silicate glass, quartz glass or in which at least two
Mixture.
The metal oxide is preferably selected from iron (Fe), copper (Cu), gold (Au), silver (Ag), platinum (Pt), palladium (Pd), titanium
(Ti), chromium (Cr), cobalt (Co), rhodium (Rh), aluminium (Al), bismuth (Bi), tin (Sn), zirconium (Zr), osmium (Os), tungsten (W) or in which at least
The oxide of the metal of two kinds of mixture.The metal oxide is preferably selected from silica, dioxy it is also preferable that pearlescent pigment
Change titanium, iron oxide (III), zirconium dioxide or in which at least two mixture.
The metal silicate is preferably selected from iron (Fe), copper (Cu), gold (Au), silver (Ag), platinum (Pt), palladium (Pd), titanium
(Ti), chromium (Cr), cobalt (Co), rhodium (Rh), aluminium (Al), bismuth (Bi), tin (Sn), zirconium (Zr), osmium (Os), tungsten (W) or in which at least
The silicate of the metal of two kinds of mixture.In addition, the silicate can be feldspar.
The ceramics can be those skilled in the art can thus purposes selection any ceramic material.The ceramic material is preferred
Selected from oxide ceramics, silicate ceramics, non-oxide ceramics or in which at least two mixture.
The oxide ceramics is preferably selected from or mixtures thereof metal oxide, quasi-metal oxide.The metal oxide
Metal can be selected from aluminium, beryllium, barium, calcium, magnesium, sodium, potassium, iron, zirconium, titanium, zinc, tin or in which at least two mixture.The metal oxygen
Compound is preferably selected from aluminium oxide (Al2O3), calcium oxide, sodium oxide molybdena, potassium oxide, magnesia (MgO), silica (SiO2), zirconium oxide
(ZrO2), yttrium oxide (Y2O3), aluminium titanates (Al2TiO5) or in which at least two mixture.The quasi- gold of the quasi-metal oxide
Belong to be preferably selected from boron, silicon, arsenic, tellurium, lead, bismuth or in which at least two mixture.
The silicate ceramics is preferably selected from steatite (Mg3[Si4O10(OH)2]) (for example, talcum form), cordierite (Mg,
Fe2+)2(Al2Si)[Al2Si4O18]), mullite (Al2Al2+2xSi2-2xO10-x, wherein x=per unit structure cell Lacking oxygen number),
Feldspar (Ba, Ca, Na, K, NH4)(Al,B,Si)4O8), kaolinite Al4[(OH)8{Si4O10] (for example, kaolin form), and
Or in which at least two mixture.The silicate ceramics is preferably porcelain.
The non-oxide ceramics can be selected from or mixtures thereof carbide, nitride.The carbide can be selected from silicon carbide
(SiC), boron carbide (B4C), titanium carbide (TiC), tungsten carbide, cementite (Fe3C).The nitride can be selected from silicon nitride (Si3N4)、
Aluminium nitride (AlN), nitrogen oxidation sial (siliconaluminiumoxinitride) (SIALON) or in which at least two it is mixed
Close object.
If the composition includes inorganic additive, the inorganic additive is preferably with the 0.1 of the total weight of the composition
Exist to 10 weight % or preferably 0.5 to 8 weight % or preferably 1 to 5 weight %.
Metal organic compound
According to the present invention, the composition further comprises metal organic compound.The metal organic compound is different from
The component i. and ii. of the composition.The metal organic compound includes at least metallic gold (Au), aluminium (Al), tin (Sn) and bismuth
(Bi).The metal of the composition can be used as metal element or metal organic compound or as metal salt or these three specified shape
The mixed form of formula exists.The organic component of the metal organic compound preferably include to have at least one, at least two or more
Multiple carbon atoms, preferably 2 to 100 preferably 4 to 50 or preferably 5 to 20 carbon atoms molecule.The organic component preferably includes
One or two or more are different from the non-metallic atom of carbon.In addition, at least one of at least one non-metallic atom
It is preferred that the metal component at least Coordination interaction with the metal organic compound, preferred ion and Coordination interaction.May be used also
To form covalent bond between at least one non-metallic atom and metal component.The non-metallic atom be preferably selected from oxygen, sulphur, nitrogen,
Phosphorus, silicon, halogen or in which at least two mixture.Preferably, in metal-organic component organic component it is described at least
One carbon atom and at least one described non-metallic atom form organic compound.
In a preferred embodiment of the composition, which includes to be selected from carbonate/ester, grass
Acid group/ester, ester, carboxylate radical/ester, halogenated carboxylic acid root/ester, hydroxycarboxylic acid root/ester, acetone acid group/ester, ketone acid root/ester, phosphoric acid
Root/ester, orthophosphite/ester, phosphide, phosphine, sulfonate radical/ester and thio resin acid group/ester or in which at least two mixing
The organic component of object.Preferably, the organic component be selected from acetate/ester, propionate/ester, butyric acid root/ester, methacrylate/ester,
Ethyl butyric acid root/ester, pentanoate/ester, caproic acid root/ester, enanthic acid root/ester, sad root/ester, isooctyl acid root/ester, n-nonanoic acid root/ester,
Capric acid root/ester, isononanoic acid root/ester, pivalate/ester, cyclohexane butyric acid root/ester, acetylacetonate, ethyl hexyl acid group/ester,
Hydracrylic acid root/ester, trifluoroacetic acid root/ester, hexafluoro -2,4- pentanedione acid group/ester；Neodecanoic acid root/ester, methanesulfonate/ester, second
Sulfonate radical/ester, propane sulfonic acid root/ester, trifluoromethanesulfonic acid root/ester, p-methyl benzenesulfonic acid root/ester, benzene sulfonic acid root/ester, natural resin, such as
Rosin or rosin acid and its derivative, such as abietate/ester, vulcanization is unsaturated natural and/or synthetic resin, such as turpentine oil,
Rosin and copaiba balsam or in which at least two mixture.
Substrate
The substrate of the layer structure, which can be those skilled in the art, to be any substrate of layer structure selection.The substrate
Be preferably selected from glass, ceramics, porcelain, ceramic tile, metal, polymer or in which at least two combination.The substrate preferably has 0.1
Millimeter is to 1 meter or preferably 0.5 millimeter to 50 centimetres or preferably 1 millimeter to 10 centimetres of thickness.The surface area of the substrate surface,
The referred to as total surface area of the substrate can be 1 to 1,000 square metre or preferably 5 to 500 square metres or preferably 10 to 200 squares
Rice.The surface of the substrate may include selected from ellipse, circle, triangle, quadrangle, polygon or in which at least two combination
Shape.The total surface area of the substrate is formed by the whole surface that can be used for applying the substrate of metal layer.
The glass be preferably selected from alkali glass, alkali-free glass, silicate glass or in which at least two mixture.The glass
It is preferably selected from soda-lime glass, lead alkali glass, borosilicate glass, alumina silicate glass, quartz glass or in which at least two
Mixture.
The ceramics can be those skilled in the art can thus purposes selection any ceramic material.The ceramic material is preferred
Selected from oxide ceramics, silicate ceramics, non-oxide ceramics or in which at least two mixture.
The oxide ceramics is preferably selected from or mixtures thereof metal oxide, quasi-metal oxide.The metal oxide
Metal can be selected from aluminium, beryllium, barium, calcium, magnesium, sodium, potassium, iron, zirconium, titanium, zinc, tin or in which at least two mixture.The metal oxygen
Compound is preferably selected from aluminium oxide (Al2O3), calcium oxide, sodium oxide molybdena, potassium oxide, magnesia (MgO), silica (SiO2), zirconium oxide
(ZrO2), yttrium oxide (Y2O3), aluminium titanates (Al2TiO5) or in which at least two mixture.The quasi- gold of the quasi-metal oxide
Belong to be preferably selected from boron, silicon, arsenic, tellurium, lead, bismuth or in which at least two mixture.
The silicate ceramics is preferably selected from steatite (Mg3[Si4O10(OH)2]) (for example, talcum form), cordierite (Mg,
Fe2+)2(Al2Si)[Al2Si4O18]), mullite (Al2Al2+2xSi2-2xO10-x, wherein x=per unit structure cell Lacking oxygen number),
Feldspar (Ba, Ca, Na, K, NH4)(Al,B,Si)4O8), kaolinite Al4[(OH)8{Si4O10] (for example, kaolin form), and
Or in which at least two mixture.The silicate ceramics is preferably porcelain.
The non-oxide ceramics can be selected from or mixtures thereof carbide, nitride.The carbide can be selected from silicon carbide
(SiC), boron carbide (B4C), titanium carbide (TiC), tungsten carbide, cementite (Fe3C).The nitride can be selected from silicon nitride (Si3N4)、
Aluminium nitride (AlN), nitrogen oxidation sial (SIALON) or in which at least two mixture.
The porcelain can be those skilled in the art can thus purposes selection any porcelain.The porcelain is preferably selected from firmly
Porcelain, porcelain tendre or combinations thereof.Hard porcelain is preferably made of 50% kaolin, 25% quartz and 25% feldspar.Porcelain tendre preferably by 25% kaolin,
45% quartz is constituted with 30% feldspar and is fired under the firing temperature lower than hard porcelain.The porcelain is preferably " china (Bone
China) " porcelain.
The ceramic tile can be those skilled in the art can thus purposes selection any ceramic tile.The ceramic tile is preferably selected from ceramics
Brick, pottery, stoneware, Shi porcelain (porcelain stoneware).
The metal can be those skilled in the art can thus purposes selection any metal.The metal be preferably selected from iron,
Steel, copper, silver, gold, platinum, palladium, bronze, brass or in which at least two mixture.
The polymer, which can be those skilled in the art, to be any polymer of layer structure selection.The polymer is preferred
It is heat-resisting.The polymer is further preferably resistant to most 500 DEG C or preferably up to 800 DEG C or preferably up to 1,000 DEG C.The polymer is preferred
Selected from epoxy resin, organosilicon, thermoplastic, rigid plastics, polyimides, polyether-ketone and polytetrafluoroethylene (PTFE).
Metal layer
The metal layer can be including metallic gold (Au), aluminium (Al), tin (Sn) and bismuth (Bi) any metal layer, wherein
In the metal layer,
The ratio of-Bi:Sn is in the range of 10:1 to 50:1；And
The ratio of-Al:Sn is in the range of 1:1 to 15:1.
Preferably, by firing composition of the invention in substrate, metal layer is generated.Just to manufacture the side of layer structure
The same way of method description carries out the firing.Preferably, firing of the composition after being applied in substrate is 500 to 1,000
DEG C or preferably 600 to 900 DEG C or preferably 700 to 850 DEG C at a temperature of carry out.It can be described in the method for just manufacturing layer structure
Same way the composition is applied in substrate.In this respect, it distinguishes and the composition is directly or indirectly applied to substrate
On to form layer structure.
The metal layer preferably includes 40 to 80 weight % of the total weight of the metal layer, preferably 45 to 75 weight % or preferably 49
To the gold of 70 weight %.It is further preferred that gold is with non-noble metal ratio in the range of 1:1 to 6:1 or preferably in 1.4:1 to 5:1
In the range of or preferably in the range of 1.6:1 to 4.5:1.Base metal should be construed as being not belonging to selected from ruthenium, rhodium, palladium,
All metals of the race of silver, osmium, iridium, platinum and gold.Noble metal and non-noble metal ratio are it is also preferred that in the range of 1:1 to 8:1
Or preferably in the range of 1.4:1 to 6:1 or preferably in the range of 1.6:1 to 5:1.Noble metal should be construed as belonging to choosing
From all metals of the race of ruthenium, rhodium, palladium, silver, osmium, iridium, platinum and gold.
The summation of all components of the metal layer adds up to 100 weight % always.
The metal layer preferably includes 0.5 to the 10 weight % or preferably 1 to 8 weight % or preferred of the total weight of the metal layer
The aluminium of 1.5 to 7 weight %.
The metal layer preferably includes 10 to the 20 weight % or preferably 12 to 19 weight % or preferred of the total weight of the metal layer
The bismuth of 13 to 18 weight %.
The metal layer preferably further include selected from platinum (Pt), palladium (Pd), rhodium (Rh), indium (In), silicon (Si), zirconium (Zr),
Osmium (Os), nickel (Ni), chromium (Cr), titanium (Ti) or in which at least two combined additional metal.The composition preferably includes to tire out
It is calculated as 1 to the 50 weight % or preferably 5 to 45 weight % of the total weight of the composition or the described of preferably 7 to 40 weight % adds
Metal.
The metal layer preferably includes platinum.The metal layer preferably include the total weight of the metal layer less than 5 weight % or excellent
Choosing is less than 4 weight % or preferably less than 3 weight % or preferably less than 2 weight % platinum.It is further preferred that in the metal layer gold with it is all
The weight ratio of the weight summation of other metals is in the range of 1:1 to 6:1 or preferably in the range of 1.5:1 to 5:1 or preferably
In the range of 2:1 to 4:1.
The metal layer preferably includes palladium.The metal layer preferably include the total weight of the metal layer less than 35 weight % or excellent
Choosing is less than 30 weight % or preferably less than 20 weight % or preferably less than 10 weight % palladiums.The metal layer preferably includes the metal layer
0.1 to 35 weight % of total weight or the palladium of preferably 1 to 30 weight % or preferably 2 to 20 weight %.
The Ni content of the metal layer is preferably the total weight of the metal layer less than 0.05 weight % or preferably smaller than 0.01 weight
Measure %.The metal layer preferably includes 0.001 to the 0.1 weight %'s or preferably 0.01 to 0.05 weight % of the total weight of the metal layer
Nickel.The metal layer is not further preferably nickeliferous.
The metal layer preferably includes 0.1 to the 5 weight % or preferably 0.2 to 4 weight % or preferred of the total weight of the metal layer
The indium of 0.3 to 3 weight %.The metal layer preferably includes 0.1 to the 10 weight % or preferably 1 to 8 weight % of the total weight of the metal layer
Or the silicon of preferably 1.5 to 7 weight %.The metal layer preferably includes 0.05 to the 5 weight % or preferably 0.2 of the total weight of the metal layer
To the zirconium of 4 weight % or preferably 0.3 to 3 weight %.The metal layer preferably include the total weight of the metal layer 0 to 1 weight % or
It is preferred that the osmium of 0.02 to 0.8 weight % or preferably 0.03 to 0.5 weight %.The metal layer preferably includes the total weight of the metal layer
0 to 1 weight % or preferably 0.02 to 0.8 weight % or preferably 0.03 to 0.5 weight % chromium.The metal layer preferably includes this
0 to 1 weight % of the total weight of metal layer or the titanium of preferably 0.02 to 0.8 weight % or preferably 0.03 to 0.5 weight %.
The metal layer being superimposed upon at least part surface of substrate preferably has 0.01 micron to 1 centimetre or preferably 0.05
Micron is to 1 millimeter or preferably 0.1 micron to 0.1 millimeter of thickness.Based on the gross area of substrate, which is preferably covered
The 1 to 100% of substrate surface or preferably 5 to 90% or preferably 10 to 80%.
The present invention is illustrated in more detail below based on the protection scope of non-limiting embodiment and attached drawing.
Specific embodiment
Carrier
The carrier (is purchased from Huntsman Inc., USA, trade name Aradur by 10 weight % polyamidoamines amides®
100), 1 weight % acetic acid (CAS 64-19-7) and 10 weight % lavender oils (CAS 8022-15-9), 5.3 weight % alkyl
Phenol resin (Tm57 to 67 DEG C), 2 weight % Crayvallac SF(be purchased from Cray Valley SA. France), 5.5
Weight % Siloxan BYK 065(is purchased from BYK Chemie GmbH, Germany) and surplus be cyclohexanol (CAS 108-
93-0) until 100 weight % are constituted.
Embodiment 1.:
The component of composition of the invention is listed in Table 1.
Table 1
The reactant of amount specified in table 1 is together with the carrier of the composition of the invention of the specified amount from embodiment 1
60 minutes are stirred at 80 DEG C by blender (Vorwerk Thermo-Mix) to generate uniform pasty mixture.It will be described
Mixture is placed in three-roll mill (Exakt®80 types are purchased from Exakt GmbH, Germany) on and pass through at least one recycle
Sufficiently homogenizing is to generate the composition.According to composition specified in the measurement table 4 and 5 of method described in chapters and sections " measurement method "
Property.Before the test, by silk-screen printing by the composition be placed on porcelain surface and electric furnace (from Naber GmbH,
Germany it is fired at 900 DEG C in).The firing includes being heated within 45 minutes 820 DEG C and sample being made to keep 10 at this temperature
Minute, hereafter trajectory (ballistic) is cooled to room temperature, and is energized wherein cutting off to the closing baking furnace.
Embodiment 2.:
The component of another composition of the invention is listed in Table 2.
Table 2
The reactant of amount specified in table 2 is together with the carrier of specified amount by blender (Vorwerk Thermo-Mix)
60 minutes are stirred at 80 DEG C to generate uniform pasty mixture.The mixture is placed in three-roll mill (Exakt® 80
Type is purchased from Exakt GmbH, Germany) on and by least one recycle sufficiently homogenizing to generate the composition.
Embodiment 3.:The component of composition of the invention is listed in Table 3.
Table 3
The reactant of amount specified in table 3 is together with the carrier of specified amount by blender (Vorwerk Thermo-Mix)
60 minutes are stirred at 80 DEG C to generate uniform pasty mixture.The mixture is placed in three-roll mill (Exakt® 80
Type is purchased from Exakt GmbH, Germany) on and by least one recycle sufficiently homogenizing to generate the composition.
Embodiment 4.4 to 5.14:
Table 4 and 5 enumerates bismuth in various compositions: tin and/or aluminium: the various ratios of tin and its property to firing composition
Influence.Embodiment 4.2 to 4.6 and 5.9 to 5.13 includes bismuth and tin with the ratio of Bi:Sn according to the present invention and Al:Sn
And aluminium.The amount of other metals is exactly equal amount listed in table 3 herein.Embodiment 4.1,4.7 and 5.8 and 5.14
Serve as reference composition.Compared with the property of composition of the invention, property, as color appearance, resistance to marring, resistance to microwave and
Dish-washing machine tolerance, which sexually revises, to be listed in table 4 and 5.Compared with the range of Bi:Sn and/or Al:Sn of the invention, the ratio of Bi:Sn
In Reference Example 4.1 and 5.8 it is lower and in Reference Example 4.7 and 5.14 it is higher.
Prepare the composition 4.1 to 4.7 from table 4 as follows based on the component from table 3: the component of composition 4.4 is just
Corresponding to amount and component from table 3.On this basis, the amount of bismuth is accordingly reduced for embodiment 4.1 to 4.3, and for reality
Apply the amount that example 4.5 to 4.7 correspondinglys increase bismuth.About remaining component of composition 4.1 to 4.7, the first row from table 3 is used
All specified amounts.In this case, in the amount and the composition of reactant respective metal score, such as the composition
Specified golden score accordingly changes.
Table 4
Sample calculates: for example, Sn the and Bi amount for calculating the composition of the embodiment 4.4 from table 4 (is rounded up to two
Digit):
13.23 %/1.8895 44.27 g * of score Al.=3.1 g
Score Sn (Al: Sn 5.67:1): 3.1 g/5.67=0.54 g
Score Bi (Bi: Sn 25:1): 0.54 g *, 25=13.5 g
Then the score of Sn and Bi is obtained to the octanoic acid for being used for correspondent composition multiplied by the metal fraction in the reactant
The amount of tin and 3- thylhexoic acid bismuth.
Table 5 is listed in each with embodiment 5.9,5.10,5.11,5.12 and 5.13 within the scope of Al:Sn according to the present invention
Kind aluminium: tin ratio.Also compare display ginseng with their property, such as color appearance, resistance to marring, resistance to microwave and dish-washing machine tolerance
Ratio 5.8 and 5.14.Their Al:Sn ratio is lower than (in the case where 5.8) or is higher than of the invention (in the case where 5.14)
Al:Sn range.
Table 5
Change the composition 5.8 to 5.14 from table 5 as follows based on the component from table 3: will be as the bismuth of reactant
Amount is down to 48.69 grams.Using with the same amount of tin of regulation in table 3.According to the specified ratio from table 5, according to the amount tune of tin
Save the amount of aluminium.On this basis, the amount of aluminium is accordingly reduced for embodiment 5.8 to 5.10, and for embodiment 5.11 to 5.14
Correspondingly increase the amount of bismuth.About remaining component of composition 5.8 to 5.14, all specified amounts of the first row from table 3 are used.
In this case, in the amount and the composition of reactant respective metal score, such as specified golden score accordingly changes.
According to the property of composition specified in the measurement table 4 and 5 of method described in chapters and sections " measurement method ".It is testing
Before, it is as follows to be described in more detail in the description of the drawings, on the decal paper, then transfer seal coat is being applied by silk-screen printing
It is applied on porcelain plate after (coming from Ferro GmbH, the L406 type of Germany) and drying, the composition is printed onto porcelain table
On face.Firing, which is included in, to be heated to 820 DEG C for 45 minutes in electric furnace (from Naber GmbH, Germany) and sample is made to exist
It is kept at a temperature of this 10 minutes, hereafter trajectory is cooling, wherein not energizing further to the closing baking furnace.Herein, ratio
" b ratio a " refers to the coefficient a and b such as measured according to laboratory method.Also illustrated in " measurement method " entry resistance to marring,
The measuring method of resistance to microwave " Mikrowellenbest. " and dish-washing machine tolerance " St.-fest ".Herein, from table 4
With 5 in it is clear that composition 4.2 to 4.6 and 5.9 to 5.13 of the invention is formed than Reference Example 4.1 and 4.7 and 5.8 Hes
5.14(they do not include metal ratios of the invention of Bi:Sn and Al:Sn) the strong yellow layer structure using porcelain.This can
To be derived by the value for being normalized to composition 4.4 and/or 5.11.Only other compositions of the invention reach standard value 1.Reference
All compositions of experiment 4.1,4.7,5.8 and 5.14 have the color of the composition of the invention significantly lower than the same table
Value.Although due to yellow value improve and improve optical property, resistance to marring, resistance to microwave and dish-washing machine tolerance with business
In the suitable range of vessel.In addition, some compositions of the invention, such as 4.5 and 4.6 include and the phase of reference composition 4.1 and 4.7
Than the dish-washing machine tolerance improved under this good color value.
Measurement method
Emission spectrographic analysis (ICP)
ICP can be used for analyzing metal Ag, Au in thickener or flowing product, B, Bi, Ca, Cr, Cu, Ni, Ir, Pd, Pt,
Rh, V, Zn, Zr, Si, Sn, Os and Ti.Varian Inc. is come from using Varian Vista-MPX() emission spectrometer.
A1. initially, by known metal content (such as 1,000 mg/litre) in the chloroazotic acid matrix (concentrated hydrochloric acid and dense nitre of 3:1
Acid) in standard solution prepare metal Ag, Au, Ir, Pd, Pt, Rh, Ru, Si, Ti, V, Sn, Zr, B, Bi, Ca, Cr, Cu, In,
Respective two calibration samples of Ni, Zn, wherein being given at amount of metal (first numerical value in 1,000 milliliter of solution with [mg/l]
Indicate the concentration of the first calibration sample, the concentration of second the second calibration sample of numerical value)
Ag 35:70
Au 50:150
Ir, Pd, Pt, Rh, Ru 15:30
Si, Ti, V, Sn, Zr 10:20
B, Bi, Ca, Cr, Cu, In, Ni, Zn 10:20
The parameter of ICP device is as follows:
Power: 1.25 kW
Plasma gas: 15.0 l/min(argon gas)
Assist gas: 1.50 l/min(argon gas)
Atomization pressure: 220 kPa(argon gas)
It repeats: 20 s
Stabilize the time: 45 s
Height of observation: 10 mm
Sample air-breathing: 45 s
Washing time: 10 s
Pump rate: 20 rpm
It repeats: 3
Wavelength [nm] for analyzing tenor is as follows:
Ag 338,29；In 303,94；Sn 181,06 520,91 325,61 189,93 546,55；Ir 254,40；
Ti 334,19；Au 197,74 263,97 336,12 242,79；Pd 229,65；V 292,40 267,59 340,46
309,31；B 208,96 360,96 Zn 206,20；249,77；Pt 203,65 334,50；Bi 223,06 214,42 Zr
343,82 306,77 217,47 349,62；Ca 396,85；Rh 249,08 422,67 343,49；Cr 205,56 369,
24 283,56；Ru 240,27；Cu 224,70 245,66 324,75 Si 251,61；Ni 216,55 288,16 231,
60。
A2. other standards of Os are prepared: firstly, the inside by known Os content (such as 0.10%) in solvent substrate
Metal-organic standard solution prepares calibration sample.
Metal: solvent strength [ppm]: Os maximum 7
Sampling: referring to a1.
30 grams of solvents are added in 0.10 +/- 0.02 gram of sample and the sample is homogenized at least 10 points in ultra sonic bath
Clock.
It is analyzed using following setting:
ICP parameter:
Power: 1.20 kW
Plasma gas: 16.5 l/min
Assist gas: 1.50 l/min
Atomization pressure: 180 kPa
It repeats: 15 s
Stabilize the time: 45 s
Height of observation: 11 mm
Sample air-breathing: 35 s
Washing time: 10 s
Pump rate: 15 rpm
It repeats: 3
Wavelength [nm :] Os 225.59 236.74.
A3. to the measurement of sample: 3 milliliters of nitric acid as specified in a1. above and 9 milliliters of HCl are added to 0.10
In micro-wave oven Anton Paar(equipment in +/- 0.02 gram of sample and by the sample: in 800-1 in Multivave 3000),
It is digested 60 minutes under 200 W.The sample of digestion is transferred in 100 milliliters of flasks using 50 volume %HCl.
A4. it is analyzed with defined parameter under a1. or a2., is which kind of metal depending on what is analyzed.
The measurement of color value
According to international standardEN ISO11664-4 is for example existed by the color value determination in CIE L*a*b* color space
In layer structure apply the composition after the composition color.Konica is used in CIE L*a*b* color space systems
Minolta spectrophotometer CM-700d(comes from Konica Minolta Sensing Europe B.V.) carry out color value survey
Amount.It is measured after with " black hole " and the calibration of whiteware plate.The spectrophotometer is placed in this case
On dry firing layer.It is each to carry out 5 measurements in total, then measure average value.
Resistance to marring
Plate with burned layer of precious metal (is coming from Naber GmbH, is burning at 820 DEG C in the electric furnace of Germany
System, cooling using 45 minute heating time, at a given temperature 10 minute retention time and trajectory) --- it is connected to metal arm
Go up and the kitchen sponge (rough surface of commercially available Scotch-Brite sponge) for loading 100 gram weights be placed on it --- on turntable
It is moved with the rotation speed of 80 rpm.Once visible white glaze light (the white glazing) under ornament, measurement rotation number is made
For the measurement of resistance to marring and/or result (as reference value).
Resistance to microwave
Using Bosch AG, the commercial microwave furnace of 700 W power of Germany manufacture measures resistance to microwave.
1. program:
A) subject material is applied on porcelain plate and burned at 820 DEG C (45 minute heating time, 10 minutes given
At a temperature of retention time)；
B) then, which tests 30 seconds at 700 W, Bosch AG, Germany in micro-wave oven.If no
See that spark forms and do not detect crackle and tone variations on precious-metal decoration after the plate is cooling, the sample quilt
It is chosen as resistance to microwave.
Dish-washing machine tolerance
Tolerance test in dish-washing machine can test the practicability of ornament.It is not shown after 500 periods
The coating of visible damage is considered dish-washing machine tolerance, and it is firm to be then considered dish-washing machine after 1000 periods of washing the dishes.
It quickly washes the dishes to test and corresponds to prior standards DIN 50275, except lower list:
The type of dish-washing machine: Miele G540 Spezial
Detergent: " Somat Reiniger " detergent (chlorine activity, alkalinity, phosphate-containing), 100 grams (rather than 30
Gram)
Wash temperature: 80 DEG C ± 2 DEG C (rather than 60 DEG C ± 2 DEG C)
Rule of thumb, a period of quickly washing the dishes is equivalent to normally washes the dishes the period according at least 30 of DIN 50275.
Only representative explanation can be just made with a large amount of consistent samples (at least 10).
Detailed description of the invention
In the accompanying drawings:
Fig. 1 a shows the schematic diagram of the layer structure of the invention with substrate and metal layer；
Fig. 1 b shows the schematic diagram of the layer structure of the invention with substrate, metal layer and protective layer or seal coat；
Fig. 2 a shows the schematic diagram of the substrate with the decal paper including being applied to composition of the invention thereon；
Fig. 2 b shows the schematic diagram of the precursor of the invention with composition of the invention；
Substrate and carrier structure Fig. 3 a of the invention before being shown in the decal paper that application includes composition of the invention
The schematic diagram of (decal paper)；
Fig. 3 b is shown in the schematic diagram of precursor of the invention when applying from the decal paper of Fig. 3 a；
Fig. 3 c shows the signal of the precursor of the invention with composition and protective layer and/or seal coat of the invention
Figure；
Fig. 4 shows the schematic diagram of the precursor of the invention with various layers；
Fig. 5 shows the figure that the method for layer structure of the invention is manufactured by composition of the invention.
Fig. 1 a shows the schematic diagram of layer structure 100 of the invention.Layer structure 100 includes having the substrate on surface 12
10.Substrate 10 is porcelain plate in this example.Metal layer 20 is applied on the surface 12 of substrate 10.The thickness of metal layer 20 is at this
It is 0.1 micron in example.Metal layer 20 is applied according to the method for the present invention by composition 40 of the invention as shown in figure 3b
Onto substrate 10, and impose heat treatment.Composition 40 for this purposes is equivalent to the embodiment from embodiment group 1,2 or 3
One of.
Fig. 1 b shows another layer structure 100 of the invention.Different from the layer structure 100 from Fig. 1 a, Fig. 1 b is come from
Layer structure 100 also include protective layer 56 and/or seal coat 58.If the layer structure includes that protective layer 56 and covering apply
Layer 58, seal coat 58 are preferably layer outwardly.
Fig. 2 a shows the precursor 204 of layer structure 100.Precursor 200 includes the carrier of 55 form of substrate 10 and decal paper
Structure 300.Carrier structure 300 includes layer 40, fusible separating layer 54 and the carrier layer 50 of the form of composition 40 of the invention.
Carrier layer 50 preferably includes Paper or cardboard as paper layer 50.Paper layer 50 is preferably with 200 microns of thickness.Fusible separating layer 54 is excellent
Select the thickness with 2 microns.Fusible separating layer 54 preferably includes paraffin.Precursor 200 is in heating stepses 60 for example at 60 DEG C
Heat treatment 30 minutes.
As shown in figure 2b, carrier layer 50 is then removed from precursor 200 so that precursor 200 with remaining separating layer 54 together
It only include substrate 10 and composition 40.The precursor 200 can be handled in furnace in the case where being higher than 500 DEG C, preferably 820 DEG C to generate
Layer structure 100 of the invention as shown in fig. 1A.
Fig. 3 a shows the substrate 10 with surface 12, disposes the carrier structure 300 of 55 form of decal paper on it.The applique
Paper includes the carrier layer 50 being preferably made of paper, preferably the water-soluble layer 52 made of dextrin, composition 40 of the invention and is selected from
At least one layer of the combination of protective layer 56 or seal coat 58 or both.Seal coat 58 also referred to as shifts seal coat simultaneously
It is preferred that being made of 30 microns of total thickness degree of PMMA polymer.
Fig. 3 b is shown in the carrier structure 300 after dissolving step 70.In dissolving step 70, using water, by make its with
Paper 50 and therefore also contacted with water-soluble separating layer 52, carrier layer 50 is removed from composition 40 together with separating layer 52.It borrows
Composition 40 and seal coat 58 and/or protective layer 56 can be arranged in substrate 10 by this together.This preferably by push rod 59 into
Row.Push rod 59 is preferably made of rubber.The organic transfer seal coat and composition 40 of seal coat 58 in this example with
Less than the surface 12 of the 50% degree covering substrate 10 of the total surface of substrate 10.Composition 40, carrier layer 50 and separating layer 52
Thickness is also respectively most 50 microns.Similarly, seal coat 58 and protective layer 56 preferably have most 100 microns of thickness
Degree.
Fig. 3 c shows precursor 200 of the invention obtained by 300 metastatic composition 40 of carrier structure.In this example, preceding
Body 200 is including, for example, the substrate 10 of porcelain plate form and composition 40 and protective layer 56 of the invention as be shown in the examples and covers
Lid coating 58.To as described in from the precursor 200 of Fig. 2 b, it is of the invention to obtain that the precursor from Fig. 3 c can also be heated above
Layer structure 100.Layer structure 100 obtained from precursor 200 shown in Fig. 3 c is equivalent to the layer structure from Fig. 1 b.
Before Fig. 4 is shown in the carrier structure 300 for applying the decal paper form with multiple layers (40,50,52,56,58)
Substrate 10.This is related to including water-soluble layer 52(composition 40 is placed on it) carrier structure 300.Glass frit form it is organic
Layer 56 and come from Ferro GmbH, soluble layer 58 is not located at composition 40 to the water of the L406 type seal coat form of Germany
On.
Fig. 5 schematically shows the various steps of method of the invention.In step S1 30, substrate is provided on a moving belt
10, for example, porcelain plate form.In step 2:32, composition 40 can be applied to substrate 10 directly or in indirect method
On.
Directly print an example (wherein composition 40 of the invention is applied directly on the surface of substrate 10) for method
It is for example above-mentioned silk screen print method.In the silk screen print method, per cm using Fleischle manufacture has 140 fibers
The silk screen containing polyester webs composition 40 is added to the surface 12 of substrate 10 via the silk screen wherein in step 2. 32
On.Thus using the plastic scrapers with 75-90 Shore hardness.
Alternatively, composition 40 can be applied by indirect method.The carrier structure 300 of 55 form of decal paper is used thus.Patch
Marble paper 55 comprising the carrier layer 50 being made of paper, applies such as dextrin layer 52 at the beginning on it.Apply this on dextrin layer 52
The composition 40 of invention or a variety of compositions 40 of the invention, such as according to embodiment group 1 to 3.Screen printing can for example be passed through
Brush applies a kind of composition 40 and/or numerous compositions 40.The transfer seal coat of 58 form of seal coat is applied to combination
On object 40.Dextrin layer constitutes the separating layer 52 in this case.By carrier layer 50, separating layer 52, composition 40 and seal coat
This arrangement made of 58 forms decal paper 55 as shown in fig. 3a.Then by dissolving dextrin layer 52 from the applique with water
The paper is removed on paper 55, wherein it is fixed in situ to be capped coating 58 for composition 40.Then by decal paper 55 via therefrom dissolving
That side of the paper is shifted onto substrate 10 via that side with composition 40.Then using water dissolution dextrin layer 52 so that by
It shifts the fixed composition 40 of seal coat 58 and contacts substrate 10.
In directly or indirectly method, composition 40 all preferably comprises the viscosity of 500 to 50,000 mPa*s.Thus to obtain figure
The precursor 200 of type shown in 2b or 3c.Composition 40 can be any combination object 40 from embodiment group 1,2 or 3.?
In step S3. 34, precursor 200 is imposed 800 in Nabertherm GmbH, the electric furnace or gas chamber furnace of Germany manufacture
Processing at a temperature of DEG C 1 hour.Thus to obtain layer structure 100 of the invention as shown in Fig. 1 a or 1b.
Label list
10 substrates
12 surfaces
20 metal layers
30 step S1.
32 step S2.
34 step S3.
40 compositions
50 carrier layers/paper layer
52 water-soluble layer/separating layers
54 meltable layers/separating layer
55 decal papers
56 inorganic layers/protective layer
58 water not soluble layer/seal coat
59 push rods
60 heating stepses
70 dissolving steps
100 layer structures
200 precursors
300 carrier structures
Claims (24)
1. a kind of composition (40), includes as component
I. organic carrier；
Ii. if applicable, inorganic additive；
It iii. include the metal organic compound of metallic gold (Au), aluminium (Al), tin (Sn) and bismuth (Bi)；
Wherein
The ratio of-Bi:Sn is in the range of 10:1 to 50:1；And
The ratio of-Al:Sn is in the range of 1:1 to 15:1.
2. composition (40) according to claim 1, wherein the composition (40) includes the gross weight relative to composition (40)
Measure the aluminium of 0.03 to 10 weight %.
3. composition (40) according to claim 1, wherein the composition includes the total weight relative to composition (40)
The bismuth of 0.05 to 15 weight %.
4. composition (40) as claimed in one of claims 1-3, wherein the composition (40) includes relative to composition
(40) total weight is less than the platinum of 5 weight %, and the golden weight with the weight summation of all other metal in the composition (40)
Ratio is measured in the range of 1:1 to 6:1.
5. composition (40) as claimed in one of claims 1-3, wherein total weight of the Ni content relative to composition (40)
Less than 0.05 weight %.
6. composition (40) as claimed in one of claims 1-3, wherein range of the ratio of Bi:Sn in 11:1 to 47:1
It is interior.
7. composition (40) as claimed in one of claims 1-3, wherein range of the ratio of Al:Sn in 1.1:1 to 15:1
It is interior.
8. composition (40) as claimed in one of claims 1-3, wherein the metal organic compound further comprises choosing
From palladium (Pd), rhodium (Rh), indium (In), silicon (Si), zirconium (Zr), osmium (Os), chromium (Cr), titanium (Ti) metal or in which at least two
Combination.
9. composition (40) as claimed in one of claims 1-3, wherein the organic component of the metal organic compound selects
From alcoholates, ester, ketone acid root, phosphide, mercaptide, amine and amide or in which at least two mixture.
10. composition (40) as claimed in one of claims 1-3, wherein the organic component of the metal organic compound
Selected from carboxylate radical, acetone acid group, phosphate radical, orthophosphite, phosphine, sulfonate radical and thio resin acid group or in which at least two
Mixture.
11. composition (40) as claimed in one of claims 1-3, wherein the organic component of the metal organic compound
Mixture selected from halogenated carboxylic acid root, hydroxycarboxylic acid root and oxalate or in which at least two.
12. composition (40) as claimed in one of claims 1-3, wherein the inorganic additive is selected from oxide, hydrogen-oxygen
Compound, nitrate, carbonate, sulfide, halide, sulfate, thiosulfate or in which at least two mixture.
13. composition (40) as claimed in one of claims 1-3, wherein the organic carrier is selected from organic solvent, organic
Or mixtures thereof adhesive.
14. composition (40) as claimed in one of claims 1-3, wherein the metal organic compound includes rhodium (Rh).
15. layer structure (100) comprising
I) with the substrate (10) of surface (12)；
Ii it) is at least partly superimposed upon on the surface (12) and is joined to the metal layer (20) on the surface (12)；
Wherein the metal layer (20) includes metallic gold (Au), aluminium (Al), tin (Sn) and bismuth (Bi), and wherein in the metal layer
(20) in,
The ratio of-Bi:Sn is in the range of 10:1 to 50:1；And
The ratio of-Al:Sn is in the range of 1:1 to 15:1.
16. structure (100) according to claim 15, wherein the substrate (10) is selected from glass, ceramics, porcelain, ceramic tile, gold
Belong to, polymer or in which at least two combination.
17. the precursor (200) of layer structure (100) comprising
A) with the substrate (10) of surface (12)；
B) composition (40) being superimposed upon at least part of the surface (12)；
Wherein the composition (40) include comprising metallic gold (Au), aluminium (Al), tin (Sn) and bismuth (Bi) metal-organic compound
Object；And
Wherein, in the composition (40),
The ratio of-Bi:Sn is in the range of 10:1 to 50:1；And
The ratio of-Al:Sn is in the range of 1:1 to 15:1.
18. precursor (200) according to claim 17, further comprising:
C) carrier layer (50)；With
At least one following extra play:
D) layer (54) that can be melted in the range of 40 to 80 DEG C；
E) inorganic layer (56)；
F) water not soluble layer (58).
19. layer structure (300) comprising
I. carrier layer (50)；
II. extra play (52,54), wherein the extra play (52,54) is fusing point water-soluble or with 40 to 80 DEG C；
III. composition (40) include as component
I1. organic carrier；
I2. if applicable, inorganic additive；
It i3. include the metal organic compound of metallic gold (Au), aluminium (Al), tin (Sn) and bismuth (Bi)；Wherein
The ratio of-Bi:Sn is in the range of 10:1 to 50:1；And
The ratio of-Al:Sn is in the range of 1:1 to 15:1.
20. carrier structure (300) according to claim 19, further comprises at least one following extra play:
E) inorganic layer (56)；
F) water not soluble layer (58).
21. the method for manufacturing layer structure (100) comprising step (30,32,34):
S1., the substrate (10) for having surface (12) is provided；
S2. it is superimposed composition described in claim 1 (40) at least part of the surface (12), while obtaining layer
The precursor (200) of shape structure (100)；
S3. to the precursor (200) of layer structure (100) impose at least 500 DEG C at a temperature of processing.
22. method according to claim 21, wherein the superposition in step S2. includes at least the following steps:
S4. carrier structure according to claim 19 (300,55) are provided comprising the separation with 40 to 80 DEG C of fusing point
Layer (54)；
S5. carrier structure (300,55) are superimposed at least part of the surface (12), wherein the composition (40)
It is directly contacted with the surface of substrate (10), while obtaining the precursor (200) of layer structure (100)；
S6. at least described separating layer (54) is heated to its melting temperature；
S7. carrier layer (50) and separating layer (54) are removed from precursor (200).
23. method according to claim 21, wherein the superposition in step S2. includes at least the following steps:
S8., carrier structure according to claim 19 (300,55) including water-soluble separating layer (52) is provided；
S9. carrier layer (50) are removed from the composition (40)；
S10. it is superimposed the composition (40) at least part of the surface (12), while obtaining layer structure (100)
Precursor (200).
24. wherein the processing in step S3. (34) is at 500 to 1,200 DEG C according to the method for any one of claim 21 to 23
At a temperature of carry out.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102014222996.0A DE102014222996B4 (en) | 2014-11-11 | 2014-11-11 | Composition, layer structure, their precursor, support structure, and method for producing the layer structure |
| DE102014222996.0 | 2014-11-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105585892A CN105585892A (en) | 2016-05-18 |
| CN105585892B true CN105585892B (en) | 2019-02-26 |
Family
ID=55802873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510764654.6A Active CN105585892B (en) | 2014-11-11 | 2015-11-11 | Golden clothes decorative composition and its manufacturing method with selected metal composition |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR101792351B1 (en) |
| CN (1) | CN105585892B (en) |
| DE (1) | DE102014222996B4 (en) |
| HK (1) | HK1220986A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102017007488B4 (en) | 2017-08-09 | 2021-05-12 | Carolin John | Method for refining at least one surface and an object with at least one surface |
| EP3940110A1 (en) * | 2020-07-13 | 2022-01-19 | Heraeus Deutschland GmbH & Co. KG | Preparation of noble metal complexes |
| KR102647391B1 (en) | 2021-12-24 | 2024-03-12 | 이동원 | Automatic four bundlestock device of assemble sandwich panel and urethane board |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1392890A (en) * | 2000-07-25 | 2003-01-22 | 三井化学株式会社 | Curable composition and uses thereof |
| CN1521768A (en) * | 1998-04-29 | 2004-08-18 | Ī�ٹ��ʹɷ�����˾ | Formation of thin film resistors |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT225206B (en) * | 1958-05-02 | 1963-01-10 | Meyercord Co | Vitreous transfer and process for its manufacture |
| US3481758A (en) | 1966-11-01 | 1969-12-02 | American Optical Corp | Method of coating a glass substrate |
| DE4122131C1 (en) * | 1991-07-04 | 1992-07-16 | W.C. Heraeus Gmbh, 6450 Hanau, De | Gold@ prepn., for decoration of glass and ceramics - comprise adding e.g. gold mercaptide deriv. to hot soln. of polyethylene@ wax in non-polar solvent |
| DE19704479A1 (en) | 1997-02-06 | 1998-08-13 | Cerdec Ag | Decorative preparation for the production of gold-containing decorations and their use |
| JPH11335188A (en) * | 1998-05-27 | 1999-12-07 | Naniwa Kineki Kk | Paste gold and gold-decorated article |
| ES2153708T5 (en) * | 1999-04-09 | 2006-06-01 | W.C. Heraeus Gmbh | BRIGHT PREPARATION OF NOBLE METAL. |
| DE19941020B4 (en) | 1999-08-28 | 2007-07-19 | Ferro Gmbh | Bright noble metal preparation for high temperature firing and process for the production of bright noble metal decors |
| JP2001130985A (en) * | 1999-10-29 | 2001-05-15 | Narumi China Corp | Paste platinum and platinum ornament |
| US20080003364A1 (en) | 2006-06-28 | 2008-01-03 | Ginley David S | Metal Inks |
-
2014
- 2014-11-11 DE DE102014222996.0A patent/DE102014222996B4/en active Active
-
2015
- 2015-11-10 KR KR1020150157715A patent/KR101792351B1/en active IP Right Grant
- 2015-11-11 CN CN201510764654.6A patent/CN105585892B/en active Active
-
2016
- 2016-07-20 HK HK16108608.9A patent/HK1220986A1/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1521768A (en) * | 1998-04-29 | 2004-08-18 | Ī�ٹ��ʹɷ�����˾ | Formation of thin film resistors |
| CN1392890A (en) * | 2000-07-25 | 2003-01-22 | 三井化学株式会社 | Curable composition and uses thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| HK1220986A1 (en) | 2017-05-19 |
| KR20160056300A (en) | 2016-05-19 |
| KR101792351B1 (en) | 2017-10-31 |
| DE102014222996A1 (en) | 2016-05-12 |
| DE102014222996B4 (en) | 2018-05-09 |
| CN105585892A (en) | 2016-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9388070B2 (en) | Glass or glass-ceramic composite material and method for producing same | |
| CN105585892B (en) | Golden clothes decorative composition and its manufacturing method with selected metal composition | |
| KR101963476B1 (en) | Copper Coloured Paint, A Process For Making It And Its Application | |
| EP3604258B1 (en) | Method for manufacturing a decorated semi-transparent ceramic sheet | |
| CN110451802B (en) | Mica sheet decorative ceramic glazed brick and preparation method thereof | |
| TW201843250A (en) | Coating composition containing metal particles | |
| US9217090B2 (en) | Method and system for ink jet printing images to complex contoured surfaces of ceramic and glass items such as dishware | |
| CN105585891B (en) | Platinum decorative composition and its manufacturing method with selected metal composition | |
| KR102649877B1 (en) | Formulation for application onto glass, porcelain, tiles, metals and plastic foil | |
| JP4024792B2 (en) | Precious metal preparations or glitter preparations for indirect and direct screen printing and ceramic decals made therefrom | |
| JP6667433B2 (en) | Process for producing glossy laminated structures at low temperatures | |
| TW524789B (en) | Bright noble metal preparation for high temperature firing and the use thereof for the production of bright noble metal decoration | |
| US6428880B1 (en) | Paste gold and golden ornaments | |
| CN103891689B (en) | Possesses the tubular body of decorative layer | |
| JP7216167B1 (en) | decorative composition | |
| US2610128A (en) | Silk-screen printing paste | |
| KR100325589B1 (en) | Method for transferring organic printing layer on heat resistant and nonabsorbing surface | |
| JP2001130985A (en) | Paste platinum and platinum ornament | |
| JP2003151363A (en) | Conductive film and manufacturing method of conductive film | |
| JP2023073047A (en) | Glass forming agent and use thereof | |
| JP2023096853A (en) | Ceramic products and decorative compositions | |
| CN111574243A (en) | Bright noble metal preparation and application thereof | |
| JPH1025134A (en) | Glass-coloring agent composition excellent in water resistance | |
| JP2003297147A (en) | Composition containing metal, ceramic having electrically conductive coated film and manufacturing method therefor | |
| JPH0340906A (en) | Metal oxide film substrate and its production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: DE Ref document number: 1220986 Country of ref document: HK |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |