KR20160056300A

KR20160056300A - Gold decor composition with selected metal composition as well as method for the production thereof

Info

Publication number: KR20160056300A
Application number: KR1020150157715A
Authority: KR
Inventors: 패트리지아 휴펠; 한스-미카엘 말터
Original assignee: 헤레우스 도이칠란트 게엠베하 운트 코. 카게
Priority date: 2014-11-11
Filing date: 2015-11-10
Publication date: 2016-05-19
Also published as: CN105585892A; CN105585892B; DE102014222996B4; DE102014222996A1; KR101792351B1; HK1220986A1

Abstract

The present invention provides a composition comprising: i. Organic vehicle, ii. If applicable, inorganic additives; iii. Wherein the ratio of Bi to Sn is in the range of 10: 1 to 50: 1, and the ratio of Bi (Al) to Sn (Bi) To Sn is in the range of 1: 1 to 15: 1. The present invention also provides a layered structure comprising: i. A substrate having a surface, ii. Wherein the metal layer comprises metal, gold (Au), aluminum (Al), tin (Sn) and bismuth (Bi) Wherein the ratio of Bi to Sn is in the range of 10: 1 to 50: 1 and the ratio of Al to Sn is in the range of 1: 1 to 15: 1. The present invention also relates to a precursor of a layered structure comprising a) a substrate having a surface, b) a composition at least partially superimposed on the surface, wherein the composition comprises a metal, gold (Au) Wherein the ratio of Bi to Sn in the composition is in the range of 10: 1 to 50: 1 and the ratio of Al to Sn is in the range of 1: 1 to 15: 1, wherein the metal- will be. The present invention also provides a method of producing a layered structure, comprising the steps of: S1. Providing a substrate having a surface, S2. Obtaining a precursor of a layered structure while superimposing the first composition on at least a part of the surface, S3. Treating the precursor of the layered structure at a temperature of 500 캜 or higher.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a gold decorative composition having a selected metal composition and a method for producing the same.

The present invention provides a composition comprising: i. Organic vehicle; ii. Inorganic additives, where applicable; iii. Wherein the ratio of Bi to Sn is in the range of 10: 1 to 50: 1, and the ratio of Bi (Al) to Sn (Bi) To Sn is in the range of 1: 1 to 15: 1. The present invention also provides a layered structure comprising: i. A substrate having a surface, ii. Wherein the metal layer comprises metal, gold (Au), aluminum (Al), tin (Sn) and bismuth (Bi) Wherein the ratio of Bi to Sn is in the range of 10: 1 to 50: 1 and the ratio of Al to Sn is in the range of 1: 1 to 15: 1. The present invention also relates to a precursor of a layered structure comprising a) a substrate having a surface, b) a composition at least partially superimposed on the surface, wherein the composition comprises a metal, gold (Au) Wherein the ratio of Bi to Sn is in the range of 10: 1 to 50: 1 and the ratio of Al to Sn is in the range of 1: 1 to 15: 1 in the composition. . The present invention also provides a method of producing a layered structure, comprising the steps of: S1. Providing a substrate having a surface, S2. Obtaining a precursor of a layered structure while superimposing the first composition on at least a portion of the surface; S3. Treating the precursor of the layered structure at a temperature of 500 캜 or higher.

Metal-containing compositions are used in a variety of applications. Accordingly, metal containing compositions as described in U. S. Patent Nos. 3481758 A, 2008/03364 A1 and 2013/011957 Al are commonly used to produce semiconductor devices. In addition, the metal-containing composition is used as an ornament in various objects. It is common to use metal-containing compositions to decorate objects to obtain special effects. Various compositions having different metal compositions are described, for example, in patent application DE 197 04 479 A1.

None of the above cited references are directed to the selection of metal-containing compositions, also referred to as lusters, which are suitable for providing coatings with both good decorative and excellent microwave durability.

Overall, it is an object of the present invention to at least partially solve the drawbacks which occur according to the prior art.

Another object is to provide a composition suitable for durable film formation.

Another object is to provide a composition suitable for forming a durable film in an ornamental form on a durable article, for example, in a dishwasher and microwave oven.

Another object is to provide an inexpensive composition.

Another object is to provide a composition which is capable of making decorative objects, especially glossy objects, on various objects.

Another object is to provide a composition suitable for forming a durable film of decorative form having a low noble metal content in an object, for example.

It is also an object to provide a composition which can be easily processed at low cost.

Another object is to provide a lamellar structure exhibiting the highest possible durability, especially when used in a layered structure in dishwashers and microwave ovens.

In addition, the object includes providing a method of manufacturing a layered structure in an inexpensive and time-saving manner.

It is another object to provide a method of manufacturing a layered structure that is as stable as possible.

The first subject of the present invention provides a solution to one of the above-mentioned objects. The first embodiment of the subject matter is as follows:

[1]

i. Organic vehicle,

ii. If applicable, inorganic additives,

iii. Metal-organic compounds including metals, gold (Au), aluminum (Al), tin (Sn) and bismuth (Bi)

As a component,

The ratio of Bi to Sn is in the range of 10: 1 to 50: 1,

Wherein the ratio of Al to Sn is in the range of 1: 1 to 15: 1.

Preferably, the composition according to the invention is suitable for application to an object, for example a substrate, to form a robust durable decoration on the object, preferably after heating. The composition may comprise any ingredient that a person skilled in the art chooses for this purpose. The composition is preferably in liquid or paste form. The liquid composition is preferably applied by brushing, spraying or dipping. The paste-like composition is preferably applied by screen printing, stencil printing, tampon printing or emboss printing. However, the composition may be present in powder form.

The organic vehicle according to component i. May be any organic vehicle used by the person skilled in the art in the composition according to the invention. The inorganic additives according to component ii. And iii. The properties and preferred embodiments of embodiments of vehicles, inorganic additives, and metal-organic compounds will be described in more detail below.

In a preferred embodiment of the composition, which is preferably present as an inviscid liquid, the composition comprises at least one, preferably at least two or preferably all of the following properties.

a1. The solvent content is at least 30 wt%, preferably at least 35 wt%, or preferably at least 40 wt%, based on the total weight of the composition.

a2. The binder content is in the range of 5 to 30 wt.%, Preferably 8 to 25 wt.%, Or preferably 10 to 20 wt.%, Based on the total weight of the composition.

a3. The ratio of protic solvent to aprotic solvent is in the range of 1: 100 to 100: 1, preferably 1:50 to 50: 1, and particularly preferably 1: 5 to 5: 1.

a4. The viscosity ranges from 1 to 500 mPa * s, preferably from 2 to 450 mPa * s, or preferably from 5 to 400 mPa * s.

Further, it is preferable that the composition contains at least the a4 characteristic.

Preferably, in a further preferred embodiment of the pasty composition, the composition comprises at least one, preferably at least two or preferably all of the following properties.

b1. It is preferred that the total solvent content is at least 1 wt%, preferably at least 3 wt%, or preferably at least 5 wt%, based on the total weight of the composition, and the solids content does not exceed 60 wt%.

b2. The binder content ranges from 5 to 95% by weight, preferably from 7 to 90% by weight, or preferably from 10 to 50% by weight, based on the total weight of the composition.

b3. The ratio of protic solvent to aprotic solvent is in the range of 1: 100 to 100: 1, preferably 1:50 to 50: 1, and particularly preferably 1: 5 to 5: 1.

b4. The viscosity ranges from 500 to 50,000 mPa * s, preferably from 700 to 45,000 mPa * s, or preferably from 1,000 to 40,000 mPa * s.

Further, it is preferable that the composition includes at least the characteristic b4.

Characteristics a1. To a4 is preferably applied to the substrate by a direct application process as described below.

Characteristics b1. To b4 are preferably applied to the substrate by an indirect or direct application process, preferably a printing process as described below.

The composition comprises an organic vehicle preferably in the range of 20-95%, or preferably in the range of 25-90% by weight, or preferably in the range of 30-85% by weight, based on the total weight of the composition.

The metal of the composition may be present as an elemental metal in powder form, such as, for example, a gold powder, or as a metal-organic compound, or as a metal salt or metal oxide or mixed form of such a form. The stated weight for the metal content of the composition refers to the metal weight ratio in the composition, whether purely as a pure element or as a metal-organic compound or as a salt or oxide, unless otherwise explicitly defined. The weight ratio of the portion bonded to the metal is not considered in this specification. This also applies to forming specific metal ratios with respect to each other. Similarly, only the weight ratio of metal and / or metal ions is considered, while the weight ratio of the ligand is not considered.

According to the invention, the ratio of bismuth (Bi) to tin (Sn) ranges from 10: 1 to 50: 1, or preferably from 15: 1 to 40: 1 or preferably from 20: 1 to 30: . Preferably, the composition comprises tin in the range of 0.02 to 3 wt%, or preferably 0.04 to 2.0 wt%, or preferably 0.07 to 1.5 wt%, based on the total weight of the composition.

Similarly, according to the present invention, the ratio of aluminum (Al) to tin (Sn) is in the range of 1: 1 to 15: 1 or preferably in the range of 1.1: 1 to 10: 1 or preferably 1.1: 1 to 8: 1.

Preferably, the composition comprises gold in the range of 0.1 to 40% by weight, or preferably in the range of 0.5 to 30% by weight, or preferably in the range of 1 to 20% by weight, based on the total weight of the composition. Also preferably, the ratio of gold to noble metal is in the range of 1: 1 to 6: 1, or preferably in the range of 1.4: 1 to 5: 1, or preferably in the range of 1.6: 1 to 4.5: 1. Also preferably, the ratio of noble metal to noble metal is 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. The noble metals will be understood to be all metals belonging to the group selected from ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold. The non-precious metal will be understood to be any metal that does not belong to the group selected from ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold.

The sum of all components of the composition is always at most 100% by weight.

[2] The composition according to Embodiment 1, wherein the composition comprises aluminum in a range of 0.03 to 10% by weight, or preferably 0.04 to 5% by weight, or preferably 0.05 to 2% by weight, based on the total weight of the composition.

The aluminum in the composition may be present as an elemental metal or a metal-organic compound or even a metal salt or a mixture of two or more of the foregoing forms.

[3] The composition according to any one of embodiments 1 or 2, wherein the composition is present in the range of 0.05 to 15% by weight, or preferably in the range of 0.1 to 10% by weight, or preferably in the range of 0.2 to 8% by weight, Wherein the composition comprises bismuth.

The bismuth in the composition may exist as an elemental metal or a metal-organic compound or a metal salt or a mixture of two or more thereof

[4] The composition according to any one of embodiments 1-3 wherein the composition comprises less than 5% by weight or preferably less than 4% by weight or preferably less than 3% by weight or preferably less than 2% And wherein the sum of the weights of gold to all other metals in the composition 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. &Lt; / RTI >

Preferably, the composition comprises platinum in the range of 0 to 5 wt%, or preferably in the range of 0.05 to 4 wt%, or preferably in the range of 0.1 to 3 wt%, of the total weight of the composition. The platinum in the composition may be present as an elemental metal or a metal-organic compound or additionally in the form of a metal salt or a metal oxide or a mixture of two or more of the above four types

Preferably, the composition comprises palladium. Preferably, the composition comprises less than 1% by weight, or preferably less than 0.9% by weight, or preferably less than 0.8% by weight, based on the total weight of the composition. Preferably, the composition comprises palladium in the range of 0.01 to 1% by weight, or preferably in the range of 0.05 to 0.9% by weight, or preferably in the range of 0.1 to 0.8% by weight, based on the total weight of the composition. The palladium in the composition may be present as an elemental metal or a metal-organic compound or additionally in the form of a metal salt or metal oxide or a mixture of two or more of the foregoing forms.

[5] The composition according to any one of embodiments 1-4, wherein the Ni content is less than 0.05% by weight or preferably less than 0.03% by weight or preferably less than 0.01% by weight relative to the total weight of the composition.

Preferably, the composition comprises nickel in the range of 0.001 to 0.1 wt.%, Or preferably in the range of 0.001 to 0.05 wt.%, Or preferably in the range of 0.001 to 0.01 wt.%, Of the total weight of the composition. In addition, it is preferred that the composition does not contain nickel.

[6] The method according to any one of embodiments 1-5, wherein the ratio of Bi to Sn is in the range of 11: 1 to 47: 1, or preferably in the range of 13: 1 to 46: 1 or preferably 15: : 1. &Lt; / RTI >

[7] The method according to any one of embodiments 1-3, wherein the ratio of Al to Sn is in the range of 1.1: 1 to 15: 1, or preferably in the range of 2: 1 to 13: 1 or preferably in the range of 2.5: : 1. &Lt; / RTI >

The method of any one of embodiments 1-3 wherein the metal-organic compound is selected from the group consisting of Pt, Pd, Rh, In, Si, Zr, , Osmium (Os), chromium (Cr), titanium (Ti), or a combination of two or more thereof.

The metal specified above may also be referred to as an additional metal of the composition. The additional metal may be present as an additional metal-organic compound, oxide, salt, element or mixture of such forms. The weights given below with respect to additional metals are shown excluding the metal content of further metals, unless otherwise defined, even if the additional metal is present as a metal-organic compound, oxide, salt or other compound. Preferably, the composition comprises an additional metal in the range of 0.01 to 10 wt%, or preferably in the range of 0.05 to 5 wt%, or preferably in the range of 0.07 to 4 wt%, based on the total weight of the composition. Preferably, the composition comprises palladium in the range of 0 to 1% by weight, or preferably in the range of 0.1 to 0.7% by weight, or preferably in the range of 0.2 to 0.5% by weight, based on the total weight of the composition. Preferably, And in the range of 0 to 0.5% by weight, or preferably in the range of 0.1 to 0.4% by weight, or preferably in the range of 0.1 to 0.3% by weight, based on the total weight of the composition. Preferably, the composition comprises silicon in the range of 0.01 to 2 wt.%, Or preferably in the range of 0.05 to 1 wt.%, Or preferably in the range of 0.1 to 0.7 wt.%, Based on the total weight of the composition. Preferably, the composition comprises zirconium in the range of 0.01 to 2 wt.%, Or preferably 0.02 to 1 wt.%, Or preferably 0.03 to 0.7 wt.%, Based on the total weight of the composition. Preferably, the composition comprises osmium in the range of 0 to 1 wt.%, Or preferably 0.02 to 0.8 wt.%, Or preferably 0.03 to 0.5 wt.%, Based on the total weight of the composition. Preferably, the composition comprises chromium in the range of 0 to 1 wt.%, Or preferably 0.02 to 0.8 wt.%, Or preferably 0.03 to 0.5 wt.%, Based on the total weight of the composition. Preferably, the composition comprises titanium in a range of 0 to 1 wt%, or preferably 0.02 to 0.8 wt%, or preferably 0.03 to 0.5 wt%, based on the total weight of the composition.

[9] The method according to any one of embodiments 1 to 8, wherein the organic component of the metal-organic compound is an alcoholate, oxalate, ester, carboxylate, halogen carboxylate, hydroxycarboxylate, Wherein the composition is selected from the group consisting of ketones, ketones, phosphates, phosphites, phosphides, phosphanes, sulfonates, thiolates, mercaptans, amines, amides, and sulphorazinates or mixtures of two or more thereof.

Preferably, the organic component of the metal-organic compound is mercaptan or carboxylic acid, especially ethyl hexanoic acid. Preferably, the organic component is mercaptans when the metal is selected from the group of precious metals. Preferably, the organic component is a carboxylic acid, for example ethylhexanoic acid, when the metal is selected from the group of non-noble metals.

[10] The method according to any one of Embodiments 1 to 9, wherein the inorganic additive is selected from the group consisting of oxides, hydroxides, nitrates, carbonates, sulfides, halides, sulfates, thiosulfates or a mixture of two or more thereof / RTI > Preferably, the inorganic additive is selected from the group consisting of talc, pearlescent pigment and kaolin, or a mixture of two or more thereof.

[11] The composition according to any one of embodiments 1 to 10, wherein the organic vehicle is selected from the group consisting of an organic solvent, an organic binder, or mixtures thereof.

The organic solvent is selected from the group consisting of terpenes, alicyclic or aliphatic hydrocarbons, ketones, esters such as alcohols such as ethanol, isopropanol or hexanol, or mixtures of two or more thereof. Preferably, the solvent is one of those described above.

The organic binder may be any binder used by those skilled in the art for this purpose. Preferably, the organic binder is selected from the group of binders as described in the organic vehicle.

[12] The composition of any of embodiments 1-11, wherein the metal-organic compound comprises rhodium (Rh).

Preferably, the composition comprises rhodium in the range of 0.001 to 0.1% by weight, or preferably in the range of 0.001 to 0.02% by weight, or preferably in the range of 0.001 to 0.4% by weight, based on the total weight of the composition.

Another subject of the present invention is a layered structure. The first design of the layered structure according to the present invention is presented in the following embodiments.

[13] As the layered structure,

i. A substrate having a surface,

ii. On the surface, at least in part, a superimposed metal layer

Wherein the metal layer comprises a metal, gold (Au), aluminum (Al), tin (Sn) and bismuth (Bi)

The ratio of Bi to Sn is in the range of 10: 1 to 50: 1,

Layer structure in which the ratio of Al to Sn is in the range of 1: 1 to 15: 1.

The layered structure can be in any form. Preferably, the layered structure has a shape selected from the group consisting of a circle, a corrugated shape, a cylindrical shape, a cubic shape, a rectangular shape, a conical shape, a penetration shape, a pyramidal shape, or a combination of two or more thereof. The substrate may comprise any material that a person skilled in the art uses for this purpose. Preferably, the substrate has a surface to which the metal layer can be applied. The substrate and its properties are described in more detail below. Preferably, the method according to the invention to be described below is used for application of the metal layer. Preferably, the composition according to the invention is used as a coating material for this purpose. The relative contrast of the components to each other as well as all the properties and components specified above referring to the composition according to the invention is preferably applied to the metal layer.

14. The layered structure of embodiment 13 wherein the substrate is selected from the group consisting of glass, ceramics, porcelain, tiles, metals, polymers, combinations of two or more thereof, and glass and ceramics are preferred.

Another subject of the present invention relates to precursors. The first design according to the present invention is presented in the following embodiments.

[15] As a precursor of a layered structure,

a) a substrate having a surface,

b) a composition superimposed on at least a portion of said surface

Wherein the composition comprises a metal-organic compound comprising metal, gold (Au), aluminum (Al), tin (Sn) and bismuth (Bi)

The ratio of Bi to Sn is in the range of 10: 1 to 50: 1,

A precursor in which the ratio of Al to Sn is in the range of 1: 1 to 15: 1.

The precursors of the layered structure may be any precursors that a person skilled in the art chooses for this purpose. The characteristics of the substrate will be apparent from the description of the layered structure and the description of the composition as well as the following description, and will also apply to the precursor. For a method of directly applying a composition to a substrate, reference is made to a method according to the invention for producing a layered structure.

b) Partial superposition on the surface of the substrate with the composition in the item may be a direct or indirect superposition by the composition. Direct overlay can be accomplished, for example, by printing methods, such as screen printing, tampon printing, as well as ink jet printing or spraying methods. Various methods for direct application of the composition to a substrate refer to the process of the present invention for making a layered structure. Indirect superposition is preferably carried out by a method of applying the composition by means of a decar shaped carrier structure comprising the composition. The carrier structure of the decal will be discussed in more detail below.

[16] The process of embodiment 15,

c) a carrier layer; And

The following layers:

d) a layer which can be melted in the range of 40 ° C to 80 ° C,

e) an inorganic layer,

f) water insoluble layer

&Lt; / RTI >

Embodiment 16 of the precursor comprises at least one carrier layer in addition to the substrate and composition. The carrier layer may comprise any material suitable for containing the composition without the composition being separated, transferred, spilled, or otherwise altered in its structural arrangement prior to application over the substrate. The carrier layer preferably comprises paper or cardboard. Preferably, the carrier layer comprises paper or cardboard paper in the range of 50 to 100% by weight, or preferably in the range of 70 to 100% by weight, or preferably in the range of 90 to 100% by weight, based on the total weight of the carrier structure. The carrier structure preferably has a thickness in the range of 0.5 μm to 2 mm, preferably in the range of 1 μm to 1.5 mm, or preferably in the range of 2 μm to 1 mm. The carrier structure is preferably in the range of 1 to 1,000 cm in length, or preferably in the range of 5 to 500 cm, or preferably in the range of 10 to 200 cm. Preferably, the apparatus has a width in the range of 1 to 1,000 cm, or preferably in the range of 5 to 500 cm, or preferably in the range of 10 to 200 cm. Preferably, the carrier layer has a surface area formed by the length and width in the range of 10 cm ² to 100 m ^2, or preferably in the range of 20 cm ² to 50 m ^2, or preferably 30 cm ² to 10 m ² .

The precursor preferably comprises an additional layer. The precursor of Embodiment 16 preferably comprises a first additional layer in the form of a layer which can be melted in the range of from 40 to 80 캜 and is hereinafter referred to simply as the fusible layer. The meltable layer d) serves to easily detach the carrier layer from the composition, which is why it is also referred to hereinafter as the melt separation layer. When the meltable layer d) is heated above the melting point of the meltable layer, the separation layer is easily desorbed from the composition.

In a preferred embodiment of the precursor, the precursor of Embodiment 16 comprises a molten layer d) in direct contact with the composition. Preferably, the meltable layer d) is disposed between the carrier layer and the composition.

The meltable layer d) in embodiment 16 preferably comprises a material suitable for melting by heating in the range of 40 to 80 占 폚. Preferably, the material that can be melted at between 40 and 80 DEG C is a wax, a wax-like material or a wax-containing material. The wax is preferably selected from the group of waxes specified above for the binder. Wax, and paraffin are preferable.

Embodiment 16 preferably comprises at least one second additional layer. The second additional layer may be selected from the group consisting of an inorganic layer e), a water-insoluble layer f), or a combination of the two.

The inorganic layer e) can serve both as a stabilizer of the composition and as a protection. The inorganic layer e) is preferably selected from the group consisting of glass, glass frit, ceramics or combinations thereof. The glass and ceramics may be the same as those described for the substrate.

The water insoluble layer f) mainly serves to stabilize the composition before transferring the composition to the substrate. The water insoluble layer f) preferably comprises a cover coat. Preferably, the cover coat is translucent at visible range wavelengths. Preferably, the cover coat is selected from the group consisting of an acrylic cover coat, a methacrylic resin, such as a polyacrylate or polymethyl acrylate polymer, or a mixture of two or more thereof.

In a preferred embodiment of the precursor of Embodiment 16, it is preferred to have a carrier layer c) followed by a meltable layer d) followed by a composition b). It is preferred that the composition b) has a water insoluble layer f). In a further preferred embodiment of the precursor, an inorganic layer e) in the form of a glass frit is disposed between the meltable layer d) and the water-insoluble layer f). Alternatively or additionally, the inorganic layer e) may be suitably followed by the water-insoluble layer f). In a further embodiment of the addition of the precursor, the second inorganic layer e) is additionally or alternatively disposed between the fusible layer d) and the composition b).

Another subject of the present invention relates to a carrier structure. The first design of the carrier structure according to the present invention is presented in the following embodiments:

[17] As the carrier structure,

I. Carrier layer;

II. An additional layer which is water soluble or has a melting point in the range of 40 ° C to 80 ° C;

III. As a composition,

i1. Organic vehicle,

i2. If applicable, inorganic additives,

i3. A metal-organic compound including a metal, gold (Au), aluminum (Al) tin (Sn), and bismuth (Bi)

As a component,

The ratio of Bi to Sn is in the range of 10: 1 to 50: 1,

A composition wherein the ratio of Al to Sn is in the range of 1: 1 to 15: 1

&Lt; / RTI >

The carrier structure serves to transfer the composition according to the present invention onto a substrate as known in decal form. The carrier layer may comprise any material. The carrier layer is suitable for supporting the composition without the composition being separated, moved, spilled, or otherwise altered in its structural arrangement prior to application onto the substrate. For this purpose, the carrier structure comprises several layers in order to facilitate the transfer of the support after transferring the composition to the substrate. For the design of the carrier layer as well as the composition, reference is made to the characteristics of the carrier layer in the content of the precursor in Embodiment 16. [

The additional layer may be a water-soluble layer or a meltable layer d) of the type described above in the context of the precursor in Embodiment 16. [ The additional layer has a thickness in the range of 0.5 to 200 mu m, preferably in the range of 1 to 100 mu m, or preferably in the range of 10 to 50 mu m. The design of the carrier structure may vary depending on whether the additional layer is a water soluble layer or a meltable layer.

In a preferred embodiment of the carrier structure, the carrier structure comprises a water soluble layer. The water-soluble layer preferably comprises a material suitable for dissolving in water. The water soluble layer is preferably selected from the group consisting of salts, for example carbohydrates, such as sugars, sugar analogs, or a combination of two or more of these. Salt is preferably selected from the salts (NaCl), potassium chloride (KCl), lithium chloride (LiCl), magnesium chloride (MgCl ₂₎ or the group consisting of a mixture of two or more of these. The sugar or sugar-like substance is preferably selected from the group consisting of glucose, fructose, saccharin, maltose, dextrin, maltodext, gum arabic or a mixture of two or more thereof.

In yet another further preferred embodiment, the carrier structure comprises a layer d) comprising a melting point in the range of 40 to 80 占 폚 as an additional layer. Reference is made to the features and materials of layer d) in embodiment 16 for the features and materials of layer d).

[18] The process of embodiment 17 wherein the following additional layer:

e) an inorganic layer,

f) water insoluble layer

&Lt; / RTI >

If the carrier structure comprises a water soluble layer as an additional layer, the additional layer is on the next side of the carrier layer and decomposition occurs behind the additional layer. The second additional layer may also be positioned between the aqueous layer and the composition. The second additional layer is preferably an inorganic layer e) of the type described above for the precursor in Embodiment 16. [ The features and materials may be the same as those described for the inorganic layer e) of embodiment 16. Preferably, the inorganic layer e) comprises particles. Preferably, the inorganic layer comprises 10 to 1,000 particles per cm < ^{3 &} gt ;. Preferably, the inorganic layer is a glass layer or a glass frit.

Also preferably, the carrier structure also comprises the water insoluble layer f) following the composition. The water insoluble layer f) corresponds to layer f) of Embodiment 16 in which the composition and characteristics are now also to be applied.

The composition may preferably be applied to the further layer in the form of a pattern, for example by screen printing. Preferably, the water insoluble layer and, if present, the inorganic layer are applied onto the composition by screen printing. The water soluble layer can be applied to other areas of the carrier structure. In a preferred embodiment of the carrier structure, the water-insoluble layer and, if present, the inorganic layer are both applied to the same area as the composition. In another embodiment, the water insoluble layer and the inorganic layer, if present, are applied to the entire surface of the carrier structure.

If the carrier structure comprises a meltable layer d) as an additional layer, the preferred embodiment of the carrier structure has a first meltable layer d) followed by the composition following the carrier layer. In a further preferred embodiment of the carrier structure, the second additional layer is located between the meltable layer d) and the composition b) as described above for a carrier structure having a water soluble layer. The second additional layer is preferably a glass frit.

Another subject of the present invention relates to a method for producing a layered structure. The first method implemented in accordance with the present invention is shown in the following embodiments.

[19] A method for producing a layered structure,

S1. Providing a substrate having a surface,

S2. Obtaining a precursor of the layered structure while superimposing the first composition on at least a portion of the surface,

S3. Treating the precursor of the layer structure at a temperature of 500 DEG C or higher

&Lt; / RTI >

The features of the substrate, composition, precursor and layered structure will be apparent from the information provided in connection with the object and will also apply to the method.

S1. Providing the substrate

The substrate in step S1 may be provided in any manner devised by those skilled in the art. Preferably, the substrate is suitably provided so that the surface of the substrate is easily accessible for superimposing the composition thereon. Preferably, the superposition involves a range of 1 to 100%, or preferably 5 to 90%, or preferably 10 to 80%, of the substrate relative to the entire surface of the substrate.

S2. The step of superposing the composition

In step S2, the overlap may be any overlapping method selected by a person skilled in the art for this purpose. The superposition can be either in the form of coating or plating. Preferably, superposition is achieved in the form of a process of applying the composition to a substrate. The application process, superposition, described below, is various methods of applying or plating the composition onto a substrate.

In the superposition process, the composition is superimposed on at least a portion of the substrate surface, whereby the composition is preferably applied. Preferably, superposition or application may be dipping into a composition or composition or a combination thereof. The application of the composition by the plating method can be carried out, for example, by spin coating, soaking, casting, dipping, sputtering, spraying, squeegee application, painting or printing, , Screen printing, gravure printing, offset printing or tampon printing. Preferably, the composition is applied by metering pump, screen printing or gravure printing. Preferably, the composition is applied at a humidity film thickness of from 0.5 μm to 250 μm, preferably a humidity film thickness of from 2 μm to 50 μm.

In the scope of the present invention, plating means that the composition used for plating, preferably a composition also referred to as a printing material, is applied to be superimposed on the surface by an auxiliary device such as, for example, a screen of a printing machine nozzle or screen printing unit . This can be done by various assistive devices. Thus, the printing material used for application or superposition can be sprayed, sputtered, or plated onto the surface of the substrate through a nozzle with a narrow, long hole. Other interesting methods include curtain coating and spin coating. Alternatively or additionally, the printing material used for application or superposition may be applied or printed to the substrate surface by, for example, a roll or a roller. Micro-dosing or ink-jet printing through a nozzle is known, for example, as spraying and / or sputtering methods. In this connection, the pressure can be applied to the printing material used for the application of the superposition or the printing material used for the application is simply dripped to the surface through the nozzle for application.

As a printing method, it is preferable to use a screen printing method for a gravure printing method. In a screen printing process, a screen made of a shape-stable material, such as a metal, preferably steel, a selected mesh size ceramic material or a blazing material, is placed on or on the superimposed object, such as a substrate in this case. The printing material used for application or superposition is applied onto the screen and pressed through the mesh using a squeegee. Since the screen has a pattern, different amounts of the printing material used for application or superposition can be applied to different locations of the screen. Thus, by using the shape and arrangement of the mesh, it is possible to apply an alternating area which does not contain the printing material used for the uniform film or application of the printing material used for superposition, and a region containing a lot of the printing material used for the application . Preferably, a uniform film of the printing material used for superimposition is transferred to the surface. For example, in order to obtain a predetermined structure such as a pattern by the above method, a screen mesh is partially blocked by a corresponding material (radiation layer, screen printing mold) applied so that the printing material is transferred to the substrate only in a predetermined area having an open mesh . In addition, instead of a screen, a thin film (stencil) with defined apertures can also be used to superimpose the printing material. Alternatively, for example, tampon printing may be used to provide a structured printing material for use in superimposition with the printing material transfer surface being squeezed or rolled onto the coated surface.

Depending on the viscosity and polarity of the printing material used in the superposition as well as the design of the nozzle and / or roll or roller, layers of different thickness can be applied to the desired surface of the substrate. Preferably, the layer applied in the application or superposition process has a thickness in the range of 0.5 to 100 mu m, preferably in the range of 1 to 50 mu m, particularly preferably in the range of 2 to 30 mu m. The thickness of the layer applied in the application process will hereinafter be referred to as the wet layer thickness. The wet layer thickness is determined by the material to be applied in the overlapping process. The thickness of the wet layer is measured immediately after the overlapping step.

Dipping involves, for example, passing the coated surface through a container of printing material used for application. Alternatively, the surface can be simply dipped into and removed from the printing material used for application, such as is done in dip-coating. Repetitive dipping enables coatings of different thicknesses to be obtained in the application process. In addition, the thickness of the coating is correlated with the selection of the printing material used in the application as mentioned above. By such a method, it is possible to obtain a coating conforming to a wet layer thickness in the range of 0.5 to 100 mu m, preferably in the range of 1 to 50 mu m, particularly preferably in the range of 2 to 30 mu m. It is also possible to use a combination of plating and dipping methods.

In one embodiment, the material to be printed used for application is applied through an application hole provided on the corresponding surface of the superimposed layer. The application hole is therefore preferably connected to the surface by a printing material used for application. A particular feature of the method, also known as micro-dosing, is that in this case it is possible to easily apply overlapping coatings of different thicknesses to an object, such as a substrate surface. Applicable holes can have any shape and size. This may relate, for example, to an application hole of a shape selected from the group consisting of a circle, an ellipse, an angled shape, a star shape, or a combination thereof. The application hole may have a surface area of 10 nm to 1 mm, preferably 100 nm to 0.5 mm, particularly preferably 100 nm to 100 μm. Preferably, the printing material used for application is applied to the surface through a nozzle by a pressure in the range of 2,000 to 10,000 mbar, preferably in the range of 2,500 to 5,000 mbar, particularly preferably in the range of 3,000 to 4,000 mbar. The printing material used for the superimposition may be connected to the surface of the overlapped layer so that the printing material used for the application can be prevented from falling off the surface. What can be achieved by this method is that a very homogeneous film can be applied to the surface.

Preferably, the application is carried out by a screen printing method or a gravure printing method. In the gravure printing method, the application preferably proceeds in a roll-to-roll state. In a preferably improved process, the printing material is applied through a screen or pressure cylinder during the printing process. The screen preferably comprises a frame made of steel or stainless steel. Preferably, the frame as a grid or screen disposed therein is also preferably made of stainless steel wire or high strength fiber.

In a preferably improved method, the screen has a mesh width in the range of 1 to 300 μm, preferably in the range of 2 to 200 μm, or preferably in the range of 3 to 90 μm. This corresponds to a mesh width of approximately 70 to 635 mesh, approximately 100 to 500 mesh, and approximately 200 to 400 mesh, respectively, wherein the mesh corresponds to a mesh wire / inch and / or mesh wire / 2.54 cm unit. With respect to application by screen printing, all commercially available squeegees can be used as a squeegee. Preferably, the squeegee includes a sintering material. Preferably, the squeegee includes a squeegee hardness in the range of 40 to 80 Shore A. The printing material preferably comprises a viscosity in the range of 500 to 50,000 mPa * s, or preferably in the range of 1,000 to 20,000 mPa * s.

The precursor of the layered structure is obtained after the composition is overlaid on at least a portion of the surface of the substrate in step S2.

S3. Elevated temperature treatment

In step S3, the precursor is treated at a temperature of at least 500 캜, preferably at least 600 캜, or preferably at least 800 캜. Elevated temperature treatment, also referred to as heat treatment, may proceed in any manner that a person skilled in the art may choose for this purpose. The heat treatment may be carried out using, for example, radiation or convection. Preferred methods of heat treatment include treatment in an infrared, flashlight, hot or dry, or drying furnace. Preferably, the heat treatment is performed by heating or in the urine. The heat treatment preferably includes a heating step, a holding step and a cooling step. The duration of the heating step is preferably in the range of 1 to 90 minutes, preferably in the range of 10 to 60 minutes, particularly preferably in the range of 15 to 50 minutes. The final temperature reached in the heating step is in the range of 600 to 1300 ° C, preferably in the range of 700 to 900 ° C, and particularly preferably in the range of 750 to 850 ° C. The duration of the holding step which is maintained at the final temperature is preferably in the range of 1 to 60 minutes, preferably in the range of 2 to 30 minutes, particularly preferably in the range of 10 to 15 minutes. The cooling step preferably proceeds at room temperature.

[20] In embodiment 19, the superposition in step S2 comprises at least the following steps:

S4. Providing a carrier structure according to the present invention as described above, comprising a meltable layer having a melting temperature in the range of 40 DEG C to 80 DEG C,

S5. Superimposing a carrier structure on at least a portion of the surface, wherein the first composition is in direct contact with the surface of the substrate to obtain a precursor of the layered structure,

S6. Heating at least the fusible layer to its melting temperature,

S7. Desorbing the carrier layer and the meltable layer from the precursor

&Lt; / RTI >

In the improved method, a decal-shaped carrier structure described in the content of the carrier structure according to the present invention described above is preferably applied to the substrate. The substrate may be designed in the same manner as described above for the carrier structure according to the present invention. In this improved process, the carrier structure comprises a meltable layer comprising a melting point in the range of 40 to 80 占 폚. The function of the meltable layer is to properly connect the carrier layer so that it can be separated from the composition to stabilize the composition prior to application to the substrate. The molten layer will hereinafter also be referred to as a melt separation layer. The meltable layer preferably comprises a wax containing the melting point of the above range as described above as an alternative to the carrier structure.

Preferably, the overlap in S5 is achieved by simply placing the carrier structure on the substrate surface with the surface comprising the composition. As a result, the composition and the substrate come into direct contact with the surface of the substrate. It will be understood that direct contact means that the composition and substrate are in direct contact without the additional layer being disposed therebetween. The batch process can proceed with a slight increase in pressure. Preferably, the batch process proceeds in the range of 1 to 20 kg, or preferably in the range of 2 to 18 kg, or preferably in the range of 3 to 15 kg. The pressure may be applied in any manner that a person skilled in the art may choose for this purpose. Preferably, application of pressure is required to load a heavy thing, for example a stamp. The first composition may be applied in the form of a pattern in this regard. The pattern is already defined in the carrier structure and is transferred from 1 to -1 as in decals.

In step S6, the entire precursor consisting of the substrate with at least the fusible layer, preferably the carrier structure, is heated to the fusing temperature of the fusible separation layer. Heating may be performed in any manner that a person skilled in the art may choose for this purpose. Preferably, the heating in step 6 is achieved by a method selected from the group consisting of heating in a urinary tract, heating by radiation, heating in a warm liquid container, heating by heating, or a combination of two or more of the above methods. Heating in the urinary tract may proceed in any urinary tract known to be capable of heating in the range of 40 to 80 占 폚. Heating by radiation can be carried out, for example, by IR light, UV light or a combination thereof. Heating in a warm liquid vessel can be carried out, for example, in a water bath. Heating by heating can be carried out by any heating gas selected by a person skilled in the art for this purpose, for example air, nitrogen or carbon dioxide, preferably air.

After at least heating the fusible separating layer to its melting temperature in step S6, the carrier layer and the fusible separating layer are desorbed from the precursor in step S7. In this regard, the first composition remains on the substrate. It is further preferred that the additional composition is applied on the first composition or on another surface of the substrate that has not yet contacted the first composition by an additional carrier structure. The process may be repeated several times so that different patterns of different compositions or overlapping patterns can be applied to the substrate.

As described in step S3, the composition thus coated may be treated with the substrate at a temperature of 500 占 폚 or higher, preferably 800 占 폚 or higher, or preferably 1,000 占 폚 or higher. The layered structure according to the present invention is obtained by the above method.

[21] The method of embodiment 19, wherein the overlap in step S2 comprises at least the following additional steps:

Q8. Providing a carrier structure according to the invention as described above, comprising a water soluble layer,

Q9. Desorbing the carrier layer and the water soluble layer from the composition,

S10. Obtaining a precursor of the layered structure while superimposing the first composition on at least a portion of the surface

&Lt; / RTI >

Further, the above-mentioned preferable improvement is another method of the improved manufacturing method of the layered structure according to the present invention described above. First, a carrier layer according to the present invention having a water-soluble layer, also referred to as a water-soluble separating layer, is provided in step S8. The carrier layer preferably comprises paper or cartons. As described above for the carrier structure according to the present invention, the water-soluble separating layer can comprise a wide range of water-soluble materials. Preferably, the water soluble layer comprises dextrin. Also preferably, the water soluble layer comprises dextrin in the range of from 50 to 100% by weight, or preferably from 70 to 100% by weight, or preferably from 90 to 100% by weight, based on the total weight of the water soluble layer.

Preferably, the carrier structure further comprises a water insoluble layer. Preferably, the water insoluble layer is a cover coat layer. The water insoluble layer, hereinafter also referred to as the cover coat layer, is preferably disposed in the carrier structure such that it is next to the composition opposite the carrier layer.

In step S9, the carrier layer and the water-soluble layer are removed together from the composition. In this regard, the cover coat layer prevents the composition from disintegrating. Preferably, the removal of the carrier layer and the separation layer is accomplished by contacting at least the water soluble layer with water. Also, preferably, the removal is achieved by contacting both the carrier layer and the water-soluble layer with water. Since the carrier layer is preferably made of paper, water in contact with the carrier layer penetrates the carrier layer to dissolve the water-soluble layer. As a result, the composition and the cover coat layer are desorbed together from the carrier layer and the water soluble layer and the composition is exposed. The cover coat layer preferably provides a suitable support for the composition such that the composition, together with the cover coat layer, is preferably moved by a squeegee or rubber wiper or other scraper to be pushed over the substrate. The cover coat can perform various functions in this regard. First, a support is provided on the composition during the transfer process onto the substrate. In addition, the cover coat can contain particles, such as, for example, glass frit, to protect the layered structure from scratching after processing at temperatures above 500 ° C. The layered structure can be protected from many external influences such as dishwashers and microwave ovens in this way. The cover coat layer may have the same composition and properties as the cover coat layer described above for the carrier structure according to the present invention. It is desirable to apply the additional composition to the other surface on the substrate that has not yet contacted the first composition by the first composition or further carrier structure. The process can be repeated several times so that different patterns of different compositions or overlapping patterns can be applied to the substrate. It is also possible to apply a different pattern to another carrier structure, alternatively, as described in yet another method in step S5.

As described in step S3, the thus applied composition may be treated with the substrate at a temperature of 500 占 폚 or higher, preferably 800 占 폚 or higher, or preferably 1,000 占 폚 or higher. The layered structure according to the present invention is obtained by the above method.

[22] The process of any one of embodiments 19-20 or 21, wherein the treatment in step S3 is performed at a temperature in the range of 500 ° C to 1,200 ° C, or preferably in the range of 600 ° C to 1,100 ° C, or preferably in the range of 700 ° C to 1,000 ° C &Lt; / RTI >

Vehicle

Preferably, the organic vehicle is in a liquid phase. The organic vehicle may comprise a polar organic vehicle or a non-polar organic vehicle or a mixture thereof.

Preferably, at least a portion of the organic vehicle is an organic solvent. The organic solvent may be a polar organic solvent or a non-polar organic solvent or a mixture thereof.

In addition, the polar organic solvent may be a polar protic organic solvent, a polar aprotic organic solvent, or a mixture thereof. The nonpolar organic vehicle is preferably a nonpolar organic solvent.

Preferably, the polar protic organic solvent comprises from 2 to 20 or preferably from 3 to 18, or preferably from 4 to 15, carbon atoms. In addition, the polar protic organic solvents it is preferable to contain at least one polar protic acid residues, for example, include _{-OH, -SH, -NH, -NH 2} , -COOH. Typical examples of polar protic organic solvents include alcohols, amines (the amines will be understood to be aliphatic and cycloaliphatic amines), acid amides, and carboxylic acids. It is preferably selected from the group consisting of lower alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, Refers to methanol, ethanol, propanol, butanol, methoxypropanol, ethoxypropanol, methoxyethanol, ethoxyethanol, 4-hydroxymethyl-1,3-dioxolane or a mixture of two or more thereof. In addition, the polar protic organic solvent may be selected from the group consisting of glycols, amines, acid amides, and carboxylic acids or mixtures of two or more thereof. Glycols include 1,2-ethanediol, 1,2-propanediol, 1,2,3-propanetriol (glycerol), 1,2-butanediol, 1,3-butanediol, -Butanediol, 1,2,3-butanetriol, 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 1,2,3-trihydroxybenzene Dihydroxy-2,5-dinitrobenzene, L-adrenaline, monosaccharides, disaccharides, liquid polyols, 1,1-dihydroxybenzene, 1,4-dihydroxy- , 1-tris- (hydroxymethyl) propane, 2,2-dimethylpropanediol-1,3, polyethylene glycol, preferably polyethylene glycols having repeating units ranging from 3 to 500, for example mono-1, 1,2-propylene glycol, 1,2-butylene glycol, 2,3-butylene glycol, or a mixture of two or more thereof. The amine may be selected from the group consisting of ammonia, methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, dimethylamine, diethylamine, di-n-propylamine, Propylene diamine, 1,3-propylene-diamine, di- (2-methylpiperazine, N-methylpiperazine, N-ethylpiperazine, morpholine, ethylenediamine, (2-aminoethyl) amine, ethanolamine, diethanolamine, triethanolamine, propanolamine, dipropanolamine, and tripropanolamine, or a mixture thereof. &Lt; / RTI > and mixtures thereof. The acid amide can be selected from the group consisting of formamide, acetamide, propionamide, butanamide, pentanamide, hexanamide, heptanamide, octanamide, or a mixture of two or more thereof. The carboxylic acid may be selected from the group consisting of formic acid, acetic acid, acrylic acid, oxalic acid, citric acid, benzoic acid, nicotinic acid, succinic acid, maleic acid, salicylic acid or a mixture of two or more thereof. The stated alcohol will be considered desirable. Preferably, the composition comprises a protonic solvent in the range of from 5 to 35% by weight, or preferably from 8 to 30% by weight, or preferably from 15 to 27% by weight, based on the total weight of the composition.

In addition to the polar protic organic solvent, the composition preferably comprises one or more additional aprotic organic solvents. The aprotic organic solvent may be selected from the group consisting of ketones, aldehydes, and sulfoxides, or mixtures of two or more thereof. The ketone may be selected from the group consisting of ethylene carbonate, N-methylpyrrolidone, N-ethylpyrrolidone, cyclohexanone. The aldehyde may be selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, caprylaldehyde, or a mixture of two or more thereof. The sulfoxide may be, for example, dimethylsulfoxide. Preferably, the composition comprises an aprotic solvent in the range of from 5 to 35% by weight, or preferably from 10 to 30% by weight, or preferably from 15 to 27% by weight, based on the total weight of the composition.

The organic vehicle preferably comprises a binder as an alternative or in addition to a solvent. It is also preferred that at least one additional portion of the organic vehicle is a binder. The binder may be present both as a protic organic vehicle and as an aprotic organic vehicle. The binder is usually higher in molecular weight than the organic solvent described above. Further, it is preferable that the binder is higher in viscosity than the organic solvent.

Binder

The binder may be any binder selected for the composition according to the invention. The binder is preferably selected from the group consisting of a thermoplastic polymer, a duo plastic polymer, a resin, and a wax or a mixture of two or more thereof. In this regard, they may be used alone or as a mixture of binders of various components of the type described above. The thermoplastic polymer may be selected from the group consisting of acrylonitrile-butadiene-styrene, polyamide, polyaminoamide, polylactate, polymethyl methacrylate, polycarbonate, polyethylene terephthalate, polyethylene, polypropylene, polystyrene, polyetheretherketone, Vinyl, or a mixture of two or more thereof. The duo plastic polymer may be selected from the group consisting of a melamine resin, an epoxy resin, a phenol resin, a polyester resin, or a mixture of two or more thereof. Preferably, the binder is, for example, a polyurethane, a polyacrylate, a polyester, a polyvinyl alcohol, a polysulfone or a mixture of two or more thereof.

Suzy

The resin is preferably a natural resin, a naturalized sulfurized resin such as a sulfated darmer resin, an asphalt, a colophony, a colophony, a colophony-modified resin, an amino resin, preferably based on natural, , A ketone resin, a terpene sulphide resin, or a mixture of two or more thereof.

Wax

A wax is a hydrocarbon compound which melts without decomposition at temperatures lower than 40 캜. The wax may preferably comprise fatty acids, fatty amides, polyolefin waxes, polyalkylene glycols, polyesters, paraffins, polyethylene, and copolymers or mixtures of two or more thereof.

Preferably, the binder is selected from the group consisting of polyacrylic resins, polymethacrylic resins, polyvinylpyrrolidone, cellulose ethers, such as hydroxyalkyl-, alkoxy-, and carboxyalkylcelluloses, polyamides, polyalkylene glycols, For example, polyethylene glycol, polyesters, polyacrylamides, polyaminoamides, polyvinyl acetates, polyvinyl alcohols, alkyd resins, polyamines, polyurethane resins, hydrocarbon resins, urea-formaldehyde resins, modified urea-formaldehyde resins, melamine resins , An alkyd resin, a polyurethane resin or an epoxy resin, or a mixture of two or more thereof.

Preferably, the composition comprises the binder in the range of from 5 to 35% by weight, or preferably from 10 to 30% by weight, or preferably from 15 to 27% by weight, based on the total weight of the composition. Also preferably, the composition comprises the resin in a range of from 10 to 30% by weight, or preferably from 13 to 25% by weight, or preferably from 15 to 23% by weight, based on the total weight of the composition.

The organic vehicle is preferably present in the composition in a ratio of protic to non-protic solvent preferably in the range of 1:35 to 35: 1 or preferably in the range of 1:20 to 20: 1 or preferably 1:10 to 10: 1 < / RTI > Preferably, the composition comprises a proton magnetic vehicle in the range of from 10 to 40% by weight, or preferably in the range of from 15 to 35% by weight, or preferably in the range of from 18 to 32% by weight, based on the total weight of the composition. Also preferably, the composition comprises an aprotic vehicle in the range of from 10 to 40% by weight, or preferably in the range of from 15 to 35% by weight, or preferably in the range of from 18 to 32% by weight, based on the total weight of the composition. Preferably, the composition has a viscosity in the range of 100 to 50,000 mPa * s.

Inorganic additive

The inorganic additive may be any inorganic additive used by a person skilled in the art in the composition according to the invention. The inorganic additive is preferably a solid at 20 占 폚. The inorganic additive is different in components i and iii of the composition. The inorganic additive is preferably used to improve abrasion resistance and to adjust the tread and mechanical durability on the surface. The inorganic additive may optionally be added to the composition. The inorganic additive is selected from the group consisting of glass, metal oxides, metal hydroxides, metal nitrates, metal carbonates, metal sulfides, metal halides, metal sulfates, metal thiosulfates, metal silicates, ammonium oxides, ammonium hydroxides, ammonium nitrates, ammonium sulfides, Ammonium, ammonium sulfate, ammonium thiosulfate, ammonium silicate, ceramics, or a mixture of two or more thereof.

The glass is preferably selected from the group consisting of an alkaline glass, a non-alkaline glass, a silicate glass or a mixture of two or more thereof. Preferably, the glass is selected from the group consisting of soda lime glass, lead alkaline glass, borosilicate glass, aluminum-silicate glass, quartz glass, or a mixture of two or more thereof.

The metal oxide may be at least one selected from the group consisting of Fe, Cu, Au, Ag, Pt, Pd, Ti, Cr, An oxide of a metal selected from the group consisting of aluminum (Al), aluminum (Al), bismuth (Bi), tin (Sn), zirconium (Zr), osmium (Os), tungsten . The metal oxide is a pearl light pigment, preferably a pearlescent pigment selected from the group consisting of silicon dioxide, titanium dioxide, iron oxide (III), zirconium dioxide, or a mixture of two or more thereof.

The metal silicate may be selected from the group consisting of Fe, Cu, Au, Ag, Pt, Pd, Ti, Cr, A silicate of a metal selected from the group consisting of aluminum (Al), aluminum (Al), bismuth (Bi), tin (Sn), zirconium (Zr), osmium (Os), tungsten . In addition, silicates can be feldspars.

The ceramics can be any ceramic material that a person skilled in the art chooses for this purpose. Preferably, the ceramic material is selected from the group consisting of oxide ceramics, silicate ceramics, non-oxide ceramics, or a mixture of two or more thereof.

The oxide ceramics are selected from the group consisting of metal oxides, metalloid oxides, or mixtures thereof. The metal of the metal oxide may be selected from the group consisting of aluminum, beryllium, barium, calcium, magnesium, sodium, potassium, iron, zirconium, titanium, zinc, tin or a mixture of two or more thereof. The metal oxide is preferably aluminum (Al ₂ O _3), calcium oxide, sodium oxide, potassium oxide, magnesium (MgO), silicon oxide (SiO _2), zirconium oxide (ZrO _2), yttrium oxide (Y ₂ O oxide _3), it is selected from aluminum titanate (Al ₂ TiO _5), or the group consisting of a mixture of two or more of these. The semimetal of the semi-metal oxide is preferably selected from the group consisting of boron, silicon, arsenic, tellurium, lead, bismuth, or a mixture of two or more thereof.

For example, the silicate ceramics include steatite (Mg ₃ [Si ₄ O ₁₀ (OH) ₂ ]), cordierite (Mg, Fe ²⁺ ) ₂ (Al ₂ Si) [Al ₂ Si ₄ O ₁₈ ] (Ba, Ca, Na, K, NH ₄ ) (Al, B, Si) ₄ O (Al ₂ Al ₂ ₊ _2x Si ₂ _- _2x O ₁₀ _- _x , x = oxygen vacancy per unit cell) ₈ ), for example kaolinite in the form of kaolin, Al ₄ [(OH) ₈ {Si ₄ O ₁₀ }] or a mixture of two or more thereof. The silicate ceramics are preferably magnetic.

The non-oxide ceramics may be selected from the group consisting of carbides, nitrides, or mixtures thereof. The carbide may be selected from the group consisting of silicon carbide (SiC), boron carbide (B ₄ C), titanium carbide (TiC), tungsten carbide, cementite (Fe ₃ C). The nitride may be selected from the group consisting of silicon nitride (Si ₃ N ₄ ), aluminum nitride (AlN), aluminum silicon nitride (SIALON), or a mixture of two or more thereof.

When the composition comprises an inorganic additive, the inorganic additive is preferably present in the range of 0.1 to 10% by weight, or preferably in the range of 0.5 to 8% by weight, or preferably in the range of 1 to 5% by weight, based on the total weight of the composition do.

Metal-organic compounds

According to the present invention, the composition further comprises a metal-organic compound. The metal-organic compound differs from the components i. And ii. Of the composition. The metal-organic compound includes at least a metal, gold (Au), aluminum (Al), tin (Sn), and bismuth (Bi). The metal of the composition may be present as an elemental metal or a metal-organic compound or metal salt or as a mixed form of three specified forms. The organic component of the metal-organic compound is a molecule having at least one carbon atom, preferably in the range of from 2 to 100, or preferably in the range of from 4 to 50, or preferably in the range of from 5 to 20, . It is preferable that the organic component includes one or two or more non-metallic elements different in carbon. In addition, at least one of the one or more non-metallic elements interacts with the metal component of the metal-organic compound at least by coordinate bond, preferably ionic bond and coordination bond. It is also possible that at least one covalent bond is formed between the non-metallic element and the metallic component. The non-metallic element is preferably selected from the group consisting of oxygen, sulfur, nitrogen, phosphorus, silicon, halogen or a mixture of two or more thereof. Preferably, at least one carbon atom and at least one nonmetallic atom of the organic component of the metal-organic component form an organic compound.

In a preferred embodiment of the composition, the metal-organic compound is selected from the group consisting of carbonate, oxalate, ester, carboxylate, halogen carboxylate, hydroxycarboxylate, acetonate, ketotate, phosphate, phosphite, , Sulfonates, and sulphorazinates, or a mixture of two or more thereof. Preferably, the organic component is selected from the group consisting of acetate, propionate, butanoate, isobutanoate ethylbutyrate, pentanoate, hexanoate, heptanoate, octanoate, isooctanoate, Carboxymethylcellulose, carboxymethylcellulose, carboxymethylcellulose, carboxymethylcellulose, carboxymethylcellulose, carboxymethylcellulose, carboxymethylcellulose, carboxymethylcellulose, carboxymethylcellulose, carboxymethylcellulose, carboxymethylcellulose, carboxymethylcellulose, carboxymethylcellulose, canoate, isononanoate, pivalate, cyclohexane butyrate, acetylacetonate, ethylhexanoate, hydroxypropionate, trifluoroacetate and hexafluoro-2,4-pentadionate; Examples of suitable solvents include, but are not limited to, neodecanoate, methanesulfonate, ethanesulfonate, propanesulfonate, trifluoromethanesulfonate, p-toluenesulfonate, benzenesulfonate, natural resins such as colophony or abietic acid and derivatives thereof And / or synthetic resins such as turpentine oil, colophony, and cofaiba balsam, or a mixture of two or more thereof.

Board

The layered substrate can be any substrate that a person skilled in the art selects for the layered structure. Preferably, the substrate is selected from the group consisting of glass, ceramic, magnetic, tile, metal, polymer, or a combination of two or more of these. Preferably, the substrate has a thickness in the range from 0.1 mm to 1 m, or preferably in the range from 0.5 mm to 50 cm, or preferably in the range from 1 mm to 10 cm. The surface area of the substrate surface, also referred to as the entire surface of the substrate, may be provided in the range of 1 to 1,000 m ^2, or preferably in the range of 5 to 500 m ^2, or preferably in the range of 10 to 200 m ² . The surface of the substrate may include shapes selected from the group consisting of elliptical, circular, triangular, square, polygonal, or a combination of two or more of these. The entire surface of the substrate is formed by the entire surface of the substrate accessible for application of the metal layer.

The silicate ceramics include, for example, stearate (Mg ₃ [Si ₄ O ₁₀ (OH) ₂ ]), cordierite (Mg, Fe ²⁺ ) ₂ (Al ₂ Si) [Al ₂ Si ₄ O ₁₈ ] ), mullite _{(Al 2 Al 2 + 2x Si} 2 - 2x O 10 -x, x = oxygen vacancies per unit cell), feldspar (Ba, Ca, Na, K, NH ₄₎ (Al, B, Si) ₄ O ₈ ), for example kaolinite in the form of kaolin, Al ₄ [(OH) ₈ {Si ₄ O ₁₀ }] or a mixture of two or more thereof. The silicate ceramics are preferably magnetic.

The self may be selected by any person selected by a person skilled in the art for this purpose. The magnetism is preferably selected from the group consisting of hard magnetic, soft magnetic or combinations thereof. The hard magnetic material is preferably composed of 50% kaolin, 25% quartz, and 25% feldspar. The soft magnet is preferably composed of 25% kaolin, 45% quartz, and 30% feldspar and is fired at a lower firing temperature compared to hard magnetic. Self is "Bong Chinna" self is preferable.

The tile may be any tile that a person skilled in the art may choose for this purpose. Preferably, the tile is selected from the group consisting of ceramic tile, croquetry, stone ware, magnetic stone ware.

The metal may be any metal that a person skilled in the art chooses for this purpose. Preferably, the metal is selected from the group consisting of iron, steel, copper, silver, gold, platinum, palladium, bronze, brass or a mixture of two or more thereof.

The polymer may be any polymer that a person skilled in the art chooses for the layered structure. Preferably, the polymer has heat resistance. Also preferably, the polymer has heat resistance up to 500 ° C or preferably up to 800 ° C or preferably up to 1,000 ° C. Preferably, the polymer is selected from the group consisting of epoxy resins, silicones, thermoplastics, duroplastics, polyimides, polyether ketones and polytetrafluoroethylene.

Metal layer

The metal layer may be any metal layer including metal, gold (Au), aluminum (Al), tin (Sn), and bismuth (Bi)

- The ratio of Bi to Sn is in the range of 10: 1 to 50: 1,

- The ratio of Al to Sn is in the range of 1: 1 to 15: 1.

Preferably, the metal layer is produced by firing the composition according to the invention on a substrate. The firing process proceeds in the same manner as described in connection with the method of manufacturing the layered structure. Preferably, after the composition is applied on the substrate, the firing process of the composition proceeds at a temperature in the range of from 500 to 1,000 ° C, or preferably in the range of from 600 to 900 ° C, or preferably in the range of from 700 to 850 ° C. The application of the composition onto the substrate can be carried out in the same manner as described in connection with the method of manufacturing the layered structure. In this regard, there is a difference between direct application of the composition and indirect application on the substrate for the formation of the layered structure.

Preferably, the metal layer comprises gold in the range of 40 to 80 wt.%, Preferably in the range of 45 to 75 wt.%, Or preferably in the range of 49 to 70 wt.%, Based on the total weight of the metal layer. Also preferably, the ratio of gold to noble metal is in the range of 1: 1 to 6: 1, or preferably in the range of 1.4: 1 to 5: 1, or preferably in the range of 1.6: 1 to 4.5: 1. The non-precious metal will be understood to be any metal that does not belong to the group selected from ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold. Preferably, the ratio of noble metal to non-metal is 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: The noble metals will be understood to be all metals belonging to the group selected from ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold.

The sum of all the components of the metal layer is always 100% by weight.

Preferably, the metal layer comprises aluminum in the range of 0.5 to 10 wt%, or preferably in the range of 1 to 8 wt%, or preferably in the range of 1.5 to 7 wt%, based on the total weight of the metal layer.

Preferably, the metal layer comprises bismuth in the range of 10 to 20 wt.%, Or preferably in the range of 12 to 19 wt.%, Or preferably in the range of 13 to 18 wt.%, Based on the total weight of the metal layer.

Preferably, the metal layer comprises at least one metal selected from the group consisting of Pt, Pd, Rh, In, Si, Zr, Os, Ni, ), Titanium (Ti), or a combination of two or more thereof. Preferably, the composition comprises from 1 to 50% by weight, or preferably from 5 to 45% by weight, or preferably from 7 to 4% by weight, of all of the additional metal relative to the total weight of the composition.

Preferably, the metal layer comprises platinum. Preferably, the metal layer comprises less than 5 wt%, or preferably less than 4 wt%, or preferably less than 3 wt% or preferably less than 2 wt% of platinum relative to the total weight of the metal layer. Also preferably, the ratio of the sum of the weights of gold and all other metals in the metal layer is in the range of 1: 1 to 6: 1, or preferably in the range of 1.5: 1 to 5: 1 or preferably 2: 1 to 4: 1.

Preferably, the metal layer comprises palladium. Preferably, the metal layer comprises less than 35 wt%, or preferably less than 30 wt%, or preferably less than 20 wt%, or preferably less than 10 wt%, of palladium, based on the total weight of the metal layer. Preferably, the metal layer comprises 0.1 to 35% by weight or preferably 1 to 30% by weight or preferably 2 to 20% by weight, based on the total weight of the metal layer, of palladium.

Preferably, the Ni content of the metal layer is less than 0.05 wt%, or preferably less than 0.01 wt%, based on the total weight of the metal layer. Preferably, the metal layer comprises nickel in the range of 0.001 to 0.1 wt.%, Or preferably 0.01 to 0.05 wt.%, Based on the total weight of the metal layer. In addition, it is preferable that the metal layer does not contain nickel.

Preferably, the metal layer comprises indium in the range of 0.1 to 5 wt%, or preferably 0.2 to 4 wt%, or preferably 0.3 to 3 wt%, based on the total weight of the metal layer. Preferably, the metal layer comprises silicon in the range of from 0.1 to 10% by weight, or preferably from 1 to 8% by weight, or preferably from 1.5 to 7% by weight, based on the total weight of the metal layer. Preferably, the metal layer comprises zirconium in the range of 0.05 to 5 wt%, or preferably 0.2 to 4 wt%, or preferably 0.3 to 3 wt%, based on the total weight of the metal layer. Preferably, the metal layer comprises 0 to 1 wt.%, Or preferably 0.02 to 0.8 wt.%, Or preferably 0.03 to 0.5 wt.%, Based on the total weight of the metal layer. Preferably, the metal layer comprises chromium in the range of 0 to 1 wt%, or preferably 0.02 to 0.8 wt%, or preferably 0.03 to 0.5 wt%, based on the total weight of the metal layer. Preferably, the metal layer comprises titanium in a range of 0 to 1 wt%, or preferably 0.02 to 0.8 wt%, or preferably 0.03 to 0.5 wt%, based on the total weight of the metal layer.

The metal layer superimposed on at least a part of the surface of the substrate preferably has a thickness in the range of from 0.01 μm to 1 cm or preferably in the range of from 0.05 μm to 1 mm or preferably from 0.1 μm to 0.1 mm. Preferably, the metal layer covers from 1 to 100%, or preferably from 5 to 90%, or preferably from 10 to 80%, of the substrate surface relative to the entire surface of the substrate.

Described at the end of the specification.

The invention is illustrated below in more detail on the basis of non-limiting embodiments and the scope of protection of the drawings.

Example

Vehicle

(CAS 64-19-7) and 10% by weight of Labyrinthine oil (CAS 8022-15-9), 5.3% (w / w) of polyamidoamide (trade name Aradur ^® 100) Crayvallac SF (Cray Valley SA. France), 5.5 wt% Siloxan BYK 065 (BYK Chemie GmbH, Germany), and 5 wt% alkyl phenol resin (T _m 57-67 캜) (CAS 108-93-0) such that the amount of the remaining cyclohexane is 100 wt%.

Example 1:

The components of the composition according to the invention are listed in Table 1.

For the compositions according to the invention, the ducts in the amounts specified in Table 1 in combination with the specified quantity of vehicle were stirred for 60 minutes at 80 DEG C by means of a stirrer (Vorwerk Thermo-Mix) to obtain a homogeneous paste-like mixture. The mixture was placed on a 3-roll mill ^{(type Exakt ® 80, Exakt GmbH} , Germany) to obtain a completely homogenized composition with more than one cycle. The properties of the compositions specified in Tables 4 and 5 were determined according to the method described in the Measurement Methods section. Prior to testing, the composition was placed on a magnetic surface by screen printing and fired in an electric furnace (Naber GmbH, Germany) at 900 占 폚. The calcination process consisted of heating to 820 占 폚 over a period of 45 minutes and holding the sample at the temperature, followed by carburization to room temperature by shutting off the energy supply to the closed calciner.

Example 2:

The components of the additional compositions according to the invention are listed in Table 2.

The ducts in the amounts specified in Table 2 in combination with the specified amount of vehicle were stirred for 60 minutes at 80 DEG C by a stirrer (Vorwerk Thermo-Mix) to obtain a homogeneous paste-like mixture. The mixture was placed on a 3-roll mill ^{(type Exakt ® 80, Exakt GmbH} , Germany) to obtain a completely homogenized composition with more than one cycle.

Example 3:

The components of the composition according to the invention are listed in Table 3.

The ducts in the amounts specified in Table 3 in combination with the specified amount of vehicle were stirred for 60 minutes at 80 DEG C by a stirrer (Vorwerk Thermo-Mix) to obtain a homogeneous paste-like mixture. The mixture was placed on a 3-roll mill ^{(type Exakt ® 80, Exakt GmbH} , Germany) to obtain a completely homogenized composition with more than one cycle.

Examples 4.4 to 5.14 :

Tables 4 and 5 show the ratio of bismuth to tin and / or aluminum to tin in various compositions and their effect on the properties of the fired composition. Examples 4.2 to 4.6 and Examples 5.9 to 5.13 include bismuth and tin as well as aluminum according to the invention of Bi versus Sn and Al versus Sn. The amount of other metals is exactly the same amount listed in Table 3 in this regard. Examples 5.8 and 5.14 as well as Examples 4.1 and 4.7 serve as reference compositions. The properties, e.g., color, scratch resistance, microwave durability, and dishwasher durability vary as listed in Tables 4 and 5 as compared to the properties of the composition according to the present invention. The ratio of Bi to Sn is lower in Reference Examples 4.1 and 5.8 than in the range of Bi to Sn and / or Al to Sn of the present invention and higher in Reference Examples 4.7 and 5.14.

Compositions 4.1 through 4.7 in Table 4 were prepared as follows, based on the ingredients in Table 3. The components of Composition 4.4 exactly correspond to the amounts and components in Table 3. On the basis of this, the amount of bismuth was relatively reduced in Examples 4.1 to 4.3, while it was relatively increased in Examples 4.5 to 4.7. With respect to the remaining components of compositions 4.1 through 4.7, all amounts specified in the first column of Table 3 were used. In this connection, the amount of duct in the composition and the proportion of the corresponding metal, for example the ratio of the specified gold of the composition, are changed relatively.

Sample Calculations: Representatively, from Example 4.4 of Table 4, the Sn and Bi amounts of the composition were calculated (rounded to two decimal places):

- Al ratio. 44.27 g * 13.23% / 1.8895 = 3.1 g

- Sn ratio (Al: Sn 5.67: 1): 3.1 g / 5.67 = 0.54 g

- Bi ratio (Bi: Sn 25: 1): 0.54 g * 25 = 13.5 g

The ratio of Sn and Bi was multiplied by the metal ratio of the duct to obtain the amount of tin octoate and bismuth-3-ethylhexanoate used in the composition.

Table 5 shows various ratios of aluminum to tin and Examples 5.9, 5.10, 5.11, 5.12, and 5.13 in the range according to the invention of Al to Sn. Reference Examples 5.8 and 5.14 also show comparison of properties such as light color, scratch resistance, microwave durability, and dishwasher durability. The ratio of Al to Sn is lower (5.8) or higher (5.14) than the range of Al to Sn of the present invention.

In Table 5, compositions 5.8 to 5.14 were changed as follows, based on the components of Table 3: The amount of bismuth as a duct was reduced to 48.69 g. The same amount of tin as specified in Table 3 was used. The amount of aluminum was adjusted to the amount of tin according to the ratio specified in Table 5. [ On this basis, the amount of aluminum was relatively reduced in Examples 5.8 to 5.10, while the amount of bismuth was relatively increased in Examples 5.11 to 5.14. For the remaining components of compositions 5.8 to 5.14, all amounts specified in the first column of Table 3 were used. In this regard, the amount of duct in the composition and the proportion of the metal, for example the specified gold, are varied accordingly.

The properties of the compositions specified in Tables 4 and 5 were determined according to the method described in the Measurement Methods section. Prior to testing, the composition was printed on decal paper on a magnetic surface by screen printing, followed by application of a transfer cover coat (Type L406 from Ferro GmbH, Germany) and drying, Apply to the magnetic plate as shown. The firing process was carried out by heating the furnace at 820 DEG C over a period of 45 minutes in an electric furnace (Naber GmbH, Germany), holding the sample at the temperature for 10 minutes, and then cooling the furnace &Lt; / RTI > In this regard, the ratio "b vs. a" refers to the factors a and b determined by the laboratory method. Measuring methods for scratch resistance, microwellenbest and dishwasher durability (St.-fest) are also described in the Measurement Methods section. In this connection, in Tables 4 and 5, Compositions 4.2-4.6 and Examples 5.9-5.13 of the present invention are based on reference examples 4.1 and 4.7, which do not contain the metal ratio Bi of the present invention and Sn and Al to Sn, And a darker yellow layered structure with magnetism than 5.14. This can be deduced from the values standardized in Composition 4.4 and / or 5.11. Only the other compositions of the present invention achieve a standard value of 1. All of the compositions of Reference Experiments 4.1, 4.7, 5.8, and 5.14 clearly show lower color values than the compositions of the present invention in the same table. Despite improved optical properties due to the increase in yellow color, scratch resistance, microwave durability, and dishwasher durability are quite comparable to commercially available products. In addition, some compositions according to the present invention, for example, 4.5 and 4.6, include improved dishwasher durability in the above color grades compared to reference compositions 4.1 and 4.7.

How to measure

Emission spectrometric analysis (ICP)

Analysis of metal, Ag, Au, B, Bi, Ca, Cr, Cu, Ni, Ir, Pd, Pt, Rh, V, Zn, Zr, Si, Sn, Os and Ti in paste or liquid using ICP can do. Varian Vista-MPX (Varian Inc.) emission spectrometer was used

a1. First, two calibration samples were prepared for each of metal, Ag, Au, Ir, Pd, Pt, Rh, Ru, Si, Ti, V, Sn, Zr, B, Bi, Ca, Cr, Cu, In, A metal content (eg, 1,000 mg / l) in a water-white matrix (3: 1 ratio of concentrated hydrochloric acid and concentrated nitric acid) was prepared from a known standard so that the amount of metal in 1,000 ml solvent was [mg / l] (The numbers above indicate the concentration of the first calibration sample, and the numbers after the calibration sample indicate the concentration of the second calibration sample).

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 parameters of the ICP device are as follows:

Power: 1.25 kW

Plasma gas: 15.0 l / min (argon)

Auxiliary gas: 1.50 l / min (argon)

Atomization pressure: 220 kPa (argon)

Repeat time: 20 s

Stabilization time: 45 s

Observation height: 10 mm

Sample aspiration: 45 s

Cleaning time: 10 s

Pump speed: 20 rpm

Number of iterations: 3

The wavelength [nm] for the analysis of the metal content 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. We have prepared an additional standard for Os. First, a calibration sample was prepared from an internal metal-organic standard solution of known Os content (e.g., 0.10%) in a solvent matrix.

Metal: Solvent concentration [ppm]: Os Max 7

Sample preparation: See a1.

30 g of the solvent was added to the 0.10 +/- 0.02 g sample and the sample was homogenized in the ultrasonic vessel for at least 10 minutes.

And analyzed using the following settings. ICP parameters:

Power: 1.20 kW

Plasma gas: 16.5 l / min (argon)

Auxiliary gas: 1.50 l / min (argon)

Atomization pressure: 180 kPa (argon)

Repetition time: 15 s

Stabilization time: 45 s

Observation height: 11 mm

Sample aspiration: 35 s

Cleaning time: 10 s

Pump speed: 15 rpm

Number of iterations: 3

Wavelength [nm:] Os 225.59 236.74

a3. Sample measurement: 3 ml nitric acid and 9 ml HCl were added to 0.10 +/- 0.02 g sample as mentioned in a1 above and the sample was heated in a microwave (Anton Paar, equipment: Multivave 3000) at 800-1,200 W for 60 minutes . The degraded sample was transferred to a 100 ml flask using 50 vol% HCl.

a4. The parameters specified in a1 or a2 were analyzed according to the metal being analyzed.

Colorimetric measurement

For example, after application of the composition in a layered structure, the color of the composition is defined as the color value in the CIE L * a * b * color system according to International Standard EN ISO 11664-4. The color tint was measured on a CIE L * a * b * colorimeter using a Konica Minolta spectrophotometer CM-700d (Konica Minolta Sensing Europe BV). Measurements were made after calibrating with a "black hole" and a white ceramic plate. In this regard, a spectrophotometer was placed on a dry calcined layer. And the average was calculated after a total of five measurements.

Scratch resistance

A plate with a baked noble metal layer (baked in an electric furnace (Naber GmbH, Germany) with a heating time of 8 minutes at 820 占 폚, a holding time of 10 minutes at a given temperature, and carbon cooling) A heavy weight kitchen sponge (a commercially available rough-surfaced Scotch-Brite sponge) was placed and moved at 80 rpm on a rotating disc. If white luster is visible under the ornament, the number of revolutions is defined as a measure and / or result of scratch resistance as a reference value.

Microwave durability

A microwave oven durability was measured using a commercially available microwave oven (Bosch AG, Germany) with a power of 700 W.

1. Course:

a) The test material was applied to a magnetic plate and baked at 820 [deg.] C (heating time 45 minutes, holding time 10 minutes at a given temperature)

b) Subsequently, the substrate was tested in a microwave oven 700 W (Bosch AG, Germany) for 30 seconds. After cooling the plate without spark formation, if the gap and color change were not observed in the decoration of the precious metal, the sample was regarded as having a microwave oven-durability.

Dishwasher durability

The durability test in a dishwasher allowed the practicality of the decoration to be tested. A coating that does not show visible damage after 500 cycles is considered to have dishwasher durability and is considered dishwasher-fast after 1000 cycles of dishwashing.

Rapid dishwashing tests are in accordance with the previous standard DIN 50275 with the following exceptions.

* Type of dishwasher: Miele G540 Spécial (Miele G540 Spezial)

* Detergent: "Somat Reiniger" detergent (chlorine active, alkaline, containing phosphoric acid), 100 g (instead of 30 g)

* Cleaning temperature: 80 ℃ ± 2 ℃ (instead of 60 ℃ ± 2 ℃)

According to experience, one quick cycle of dishwashing corresponds to more than 30 regular dishwashing cycles according to DIN 50275.

It can be said that only a large number (more than 10) of uniform samples are representative.

BRIEF DESCRIPTION OF THE DRAWINGS Fig.

In the drawings,

1a shows a schematic view of a layered structure according to the invention with a substrate and a metal layer.

1b shows a schematic view of a layered structure according to the invention with a substrate, a metal layer, and a protective layer or a cover coat layer.

Figure 2a shows a schematic view of a substrate having a decal comprising the composition according to the invention applied.

Figure 2b shows a schematic representation of a precursor according to the invention with a composition according to the invention.

3A shows a schematic view of a substrate and a carrier structure (decal) according to the present invention before applying a decal comprising a composition according to the present invention.

Figure 3b shows a schematic view of the precursor according to the invention during application of the decal of Figure 3a.

Figure 3c shows a schematic representation of a precursor according to the invention with a composition according to the invention and a protective layer and / or a cover coat layer.

Figure 4 shows a schematic representation of a precursor according to the invention with several layers.

5 shows a diagram of a method for producing a layered structure according to the present invention with a composition according to the present invention.

FIG. 1A shows a schematic view of a layered structure 100 according to the present invention. The layered structure 100 includes a substrate 10 having a surface 12. The substrate 10 is a magnetic plate in this embodiment. A metal layer (20) is applied to the surface (12) of the substrate (10). The thickness of the metal layer 20 of this embodiment is 0.1 mu m. The metal layer 20 is applied to the substrate from the composition 40 according to the invention according to the method according to the invention as illustrated in Fig. 3b, and is subjected to heat treatment. The composition (40) used for this purpose corresponds to one of the examples of Examples 1, 2 or 3.

1b shows another layered structure 100 according to the present invention. In contrast to the layered structure 100 of FIG. 1A, the layered structure 100 of FIG. 1B further includes a protective layer 56 and / or a cover coat layer 58. If the layered structure comprises both the protective layer 56 and the cover coat layer 58, preferably the cover coat layer 58 is the outer layer.

2a shows precursor 204 of layered structure 100. FIG. The precursor 200 includes a carrier structure 300 in the form of a substrate 10 and a decal 55. The carrier structure 300 includes a layer 40 in the form of a composition 40 of the present invention, a fusible separation layer 54, and a carrier layer 50. The carrier layer 50 preferably comprises paper or carton as the paper layer 50. Preferably, the paper layer 50 has a thickness of 200 [mu] m. Preferably, the fusible separation layer 54 has a thickness of 2 [mu] m. The fusible separating layer 54 preferably comprises paraffin wax. The precursor 200 is subjected to a heat treatment in a heating step 60, for example, at 60 DEG C for 30 minutes.

The carrier layer 50 may subsequently be desorbed from the precursor 200 along with the remaining separating layer 54 such that the precursor 200 includes only the substrate 10 and the composition 40 have. The precursor 200 is treated in the urine at temperatures above 500 ° C., preferably at 820 ° C. to obtain the layered structure 100 shown in FIG. 1a.

3a shows a substrate 10 having a surface 12 over which a carrier layer 300 in the form of a decal 55 is disposed. The decal preferably comprises a carrier layer 50 made of paper, preferably a water soluble layer 52 made of dextrin, a composition 40 according to the invention and a protective layer 56 or cover coat layer 58 or And at least one layer selected from a combination of the two. The cover coat layer 58 is also referred to as a transfer cover coat and is preferably made of a polymer having a total layer thickness of 30 占 퐉.

3B shows the carrier structure 300 after the dissolution step 70. FIG. The water soluble separating layer 52 is also contacted so that the carrier layer 50 is detached from the composition 40 together with the separating layer 52 when the water is contacted with the paper 50 in the dissolving step where water is used. With this method, the composition 40 can be disposed on the substrate 10 together with the cover coat layer 58 and / or the protective layer 56. This process is preferably carried out by the pusher 59. The pusher 59 is preferably made of rubber. The organic transfer covercoat and composition 40 of the cover coat layer 58 covers the surface 12 of the substrate 10 in less than 50% of the total surface of the substrate 10 in this embodiment. The thickness of the composition 40 of the carrier layer 50 and the thickness of the separation layer 52 are respectively at most 50 μm. Similarly, the cover coat layer 58 and the protective layer 56 preferably have a thickness of up to 100 [mu] m.

Figure 3c shows the precursor 200 of the present invention as a result of transfer of the composition 40 from the carrier structure 300. In this embodiment, the precursor 200 comprises, for example, a substrate 10 in the form of a magnetic plate, a composition 40 according to the invention described in the examples, and a protective layer 56 and a cover coat layer 58 . As described in the precursor 200 of FIG. 2B, the precursor of FIG. 3C may also be heated to obtain the layered structure 100 according to the present invention. The layered structure 100 obtained from the precursor 200 shown in FIG. 3C corresponds to the layered structure of FIG. 1B.

4 shows the substrate 10 before applying the decal shaped carrier structure 300 of the various layers 40, 50, 52, 56, 58 (300). This relates to a carrier structure 300 comprising a water soluble layer 52 in which the composition 40 is disposed. An organic layer 56 in the form of a glass frit and a water insoluble layer 58 in the form of a cover coat of type L406 (Ferro GmbH, Germany) are disposed on the composition 40.

Figure 5 schematically shows the various steps of the method according to the invention. In S1 step 30, the substrate 10 is provided on the conveyor belt, for example in the form of a magnetic plate. In step 2 (32), the composition 40 may be applied over the substrate 10 in a direct or otherwise indirect manner.

One example of the direct printing method in which the composition 40 of the present invention is applied directly to the surface of the substrate 10 is, for example, the screen printing method described above. In a screen printing process, a polyester mesh screen with 140 fibers per cm, manufactured by Fleischle, is used, and at step 32 the composition 40 is applied to the surface 12 of the substrate 10 ) Over the screen. A plastic squeegee of 75-90 Shore hardness is used for this purpose.

Alternatively, the composition 40 may be applied by an indirect method. A carrier structure 300 in the form of a decal 55 is used for this purpose. The decal 55 initially comprises a carrier layer 50 made, for example, of paper on which a dextrin layer 52 is applied. The composition (40) according to the invention and the compositions (50) according to the invention, for example according to Examples 1 to 3, are applied to the dextrin layer (52). The composition 40 and / or compositions 40 may be applied, for example, by screen printing. A transfer cover coat in the form of a cover coat layer 58 is applied over the composition 40. The dextrin layer forms the separation layer 52 in this case. This arrangement consisting of the carrier layer 50, the separation layer 52, the composition 40 and the cover coat layer 58 forms the decal 55 shown in Fig. 3A. The paper is then desorbed from the decal 55 by dissolving the deck screen layer 52 in water, whereby the composition 40 is held by the cover coat layer 58. Subsequently, the decal 55 is pushed against the substrate 10 laterally on the paper-melted side, i.e., next to the side containing the composition 40. Water is then used to dissolve the dextrin layer 52 and the composition 40 secured by the cover coat 58 is brought into contact with the substrate 10.

In both the direct and indirect methods, the composition (40) preferably comprises a viscosity in the range of 500 to 50,000 mPa * s. Thus, a precursor 200 of the type shown in Figure 2b or 3c is obtained. The composition (40) may be any one of Examples 1, 2, or 3. In step S3, the precursor 200 is treated in an electric or gas chamber (Nabertherm GmbH, Germany) at 800 DEG C for 1 hour. Accordingly, the layered structure 100 according to the present invention shown in FIG. 1A or 1B is obtained.

Reference number list
10 substrate
12 surface
20 metal layer
30 Step S1
32 S2 step
Step S3
40 composition
50 carrier layer / paper layer
52 water soluble layer / separating layer
54 Melting Layer / Separation Layer
55 decal
56 Inorganic layer / Protective layer
58 water insoluble layer / cover coat layer
59 pusher
60 heating step
70 Dissolution step
100 Layered structure
200 precursor
300 carrier structure

Claims

As the composition (40)
i. Organic vehicle,
ii. If applicable, inorganic additives,
iii. Metal-organic compounds including metals, gold (Au), aluminum (Al), tin (Sn) and bismuth (Bi)
As a component,
The ratio of Bi to Sn is in the range of 10: 1 to 50: 1,
A composition (40) wherein the ratio of Al to Sn is in the range of 1: 1 to 15: 1.

The composition (40) of claim 1, wherein the composition (40) comprises aluminum in a range of 0.03 to 10 weight percent based on the total weight of the composition (40).

The composition (40) of claim 1, wherein the composition (40) comprises bismuth in the range of 0.05 to 15 weight percent based on the total weight of the composition (40).

4. The composition (40) of any one of claims 1 to 3, wherein the composition (40) comprises less than 5% by weight of platinum relative to the total weight of the composition (40) (40) wherein the weight to weight ratio is in the range of 1: 1 to 6: 1.

4. The composition (40) of any one of claims 1 to 3, wherein the Ni content is less than 0.05% by weight based on the total weight of the composition (40).

4. The composition (40) according to any one of claims 1 to 3, wherein the ratio of Bi to Sn is in the range of 11: 1 to 47: 1.

4. The composition (40) according to any one of claims 1 to 3, wherein the ratio of Al to Sn is in the range of 1.1: 1 to 15: 1.

4. The method according to any one of claims 1 to 3, wherein the metal-organic compound is selected from the group consisting of platinum (Pt), palladium (Pd), rhodium (Rh), indium (In), silicon (Si), zirconium (Zr) (Os), chromium (Cr), titanium (Ti), or a combination of two or more thereof.

4. The process of any one of claims 1 to 3, wherein the organic component of the metal-organic compound is selected from the group consisting of an alcoholate, an oxalate, an ester, a carboxylate, a halogen carboxylate, a hydroxycarboxylate, an acetonate, (40), wherein the phospholipid is selected from the group consisting of phosphates, phosphites, phosphides, phosphanes, sulfonates, thiolates, amines, amides and sulphorazinates, or mixtures of two or more thereof.

4. The method according to any one of claims 1 to 3, wherein the inorganic additive is selected from the group consisting of oxides, hydroxides, nitrates, carbonates, sulfides, halides, sulfates, thiosulfates or mixtures of two or more thereof Composition (40).

4. The composition (40) according to any one of claims 1 to 3, wherein the organic vehicle is selected from the group consisting of organic solvents, organic binders, or mixtures thereof.

4. The composition (40) of any one of claims 1 to 3, wherein the metal-organic compound comprises rhodium (Rh).

As the layered structure 100,
i. The substrate 10 with the surface 12,
ii. A metal layer (20), superimposed and connected at least partially, on the surface (12)
And the metal layer 20 includes metal, gold (Au), aluminum (Al), tin (Sn), and bismuth (Bi)
The ratio of Bi to Sn is in the range of 10: 1 to 50: 1,
A layered structure (100) in which the ratio of Al to Sn is in the range of 1: 1 to 15: 1.

14. The layered structure (100) of claim 13, wherein the substrate (10) is selected from the group consisting of glass, ceramics, porcelain, tiles, metals, polymers, or a combination of two or more of these.

As the precursor 200 of the layered structure 100,
a) a substrate 10 having a surface 12,
b) a composition (40) superimposed on at least a portion of said surface (12)
, Composition 40 comprises a metal-organic compound comprising metal, gold (Au), aluminum (Al), tin (Sn) and bismuth (Bi)
The ratio of Bi to Sn is in the range of 10: 1 to 50: 1,
A precursor (200) in which the ratio of Al to Sn is in the range of 1: 1 to 15: 1.

16. The method of claim 15,
c) a carrier layer (50); And
The following additional layers:
d) a layer (54) which can be melted in the range of 40 ° C to 80 ° C,
e) an inorganic layer 56,
f) Water insoluble layer (58)
(200). &Lt; / RTI >

As carrier structure 300,
I. Carrier layer 50;
II. An additional layer (52, 54) which is water-soluble or has a melting point in the range of 40 ° C to 80 ° C;
III. As the composition (40)
i1. Organic vehicle,
i2. If applicable, inorganic additives,
i3. Metal-organic compounds including metals, gold (Au), aluminum (Al), tin (Sn) and bismuth (Bi)
As a component,
The ratio of Bi to Sn is in the range of 10: 1 to 50: 1,
- composition (40) wherein the ratio of Al to Sn is in the range of 1: 1 to 15:
&Lt; / RTI >

18. The method of claim 17, further comprising:
e) an inorganic layer 56,
f) Water insoluble layer (58)
(300). &Lt; / RTI >

A method of making a layered structure (100) comprising the steps of: (30,32,34)
S1. Providing (30) a substrate (10) having a surface (12)
S2. (32) of obtaining a precursor (200) of the layered structure (100) while superimposing the first composition (40) on at least a portion of the surface (12)
S3. A step (34) of treating the precursor (200) of the layered structure (100)
&Lt; / RTI >

20. The method of claim 19, wherein the overlap in step S2 comprises at least the following steps:
S4. Providing a carrier structure (300, 55) according to claim 17, comprising a separating layer (54) comprising a melting point in the range of from 40 캜 to 80 캜,
S5. Superimposing carrier structures 300 and 55 on at least a portion of the surface 12 such that the first composition 40 is in direct contact with the surface 12 of the substrate 10, To obtain a precursor (200)
S6. Heating at least the separating layer 54 to its melting temperature,
S7. Removing the carrier layers 300 and 55 and the separation layer 54 from the precursor 200
&Lt; / RTI >

20. The method of claim 19, wherein the overlap in step S2 comprises at least the following steps:
Q8. Providing a carrier structure (300, 55) according to claim 17, comprising a water soluble separating layer (52)
Q9. Desorbing the carrier layer 50 from the composition 40,
S10. Obtaining precursor (200) of layered structure (100) while superimposing first composition (40) on at least a portion of surface (12)
&Lt; / RTI >

22. The method according to any one of claims 19 to 21, wherein the processing in step S3 (34) proceeds at a temperature in the range of 500 [deg.] C to 1,200 [deg.] C.