WO2017091106A1 - Method of manufacturing a multi-layered valuable item with a fluorescent-type security element and multi-layered valuable item - Google Patents

Method of manufacturing a multi-layered valuable item with a fluorescent-type security element and multi-layered valuable item Download PDF

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Publication number
WO2017091106A1
WO2017091106A1 PCT/RU2016/000758 RU2016000758W WO2017091106A1 WO 2017091106 A1 WO2017091106 A1 WO 2017091106A1 RU 2016000758 W RU2016000758 W RU 2016000758W WO 2017091106 A1 WO2017091106 A1 WO 2017091106A1
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Prior art keywords
electrolyte
layered
phosphor
protective
marking
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PCT/RU2016/000758
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French (fr)
Russian (ru)
Inventor
Аркадий Владимирович ТРАЧУК
Андрей Борисович КУРЯТНИКОВ
Георгий Валентинович КОРНИЛОВ
Елена Михайловна ФЕДОРОВА
Алексей Борисович АКИНИН
Сергей Никитович ГОНЧАРОВ
Сергей Сергеевич МОИСЕЕВ
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Акционерное общество "Гознак" (АО "Гознак")
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Publication of WO2017091106A1 publication Critical patent/WO2017091106A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44F—SPECIAL DESIGNS OR PICTURES
    • B44F1/00—Designs or pictures characterised by special or unusual light effects
    • B44F1/08—Designs or pictures characterised by special or unusual light effects characterised by colour effects
    • B44F1/10—Changing, amusing, or secret pictures
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06K—GRAPHICAL DATA READING; PRESENTATION OF DATA; RECORD CARRIERS; HANDLING RECORD CARRIERS
    • G06K19/00—Record carriers for use with machines and with at least a part designed to carry digital markings
    • G06K19/06—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code
    • G06K19/08—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code using markings of different kinds or more than one marking of the same kind in the same record carrier, e.g. one marking being sensed by optical and the other by magnetic means
    • G06K19/10—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code using markings of different kinds or more than one marking of the same kind in the same record carrier, e.g. one marking being sensed by optical and the other by magnetic means at least one kind of marking being used for authentication, e.g. of credit or identity cards
    • G06K19/14—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code using markings of different kinds or more than one marking of the same kind in the same record carrier, e.g. one marking being sensed by optical and the other by magnetic means at least one kind of marking being used for authentication, e.g. of credit or identity cards the marking being sensed by radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal

Definitions

  • the invention relates to multilayer products containing metal and protective layers for protection against counterfeiting, in particular, to the production of multilayer metal products made of different materials, protected from counterfeiting, such as, for example, exchange or collection precast coins, metal tokens, medals, as well as to the original and high-precision method of their manufacture.
  • a multilayer coin-like product is known from the prior art, in particular, a token containing coding elements in the form of a layer of a luminescent substance RU 2121285 C1. Coding elements in this product provide an increase in the degree of protection against counterfeiting.
  • a multilayer product containing at least one metal and / or polymer base layer and an additional layer with coding elements, characterized in that the additional layer is made in the form a layer of a coloring matter that forms a two-dimensional QR code and is placed on the surface of the multilayer product (RU 134483, B32B 15/04 2013).
  • a multilayer metal product containing a metal selected from the range of aluminum, titanium, tantalum, niobium, with the upper surface layer subjected to electrochemical processing (RU 99379 B32B 15/00, 2010).
  • the disadvantage is the low degree of security, which is eliminated in the claimed invention through the use of a phosphor enclosed in a transparent shell, which is deposited during galvanization of the product.
  • the technical result is an increase in the degree of security, achieved by the fact that the method of manufacturing a multilayer valuable product with a protective element of a luminescent type, including immersing the product with using rod holders in a bath for plating a metal coating, equipped with anodes of the metal necessary for the deposition process, into which it is either pyrophosphate, or sulfate, or iron-hydrogen, or polyphosphate, or rhodanic, or iodide, or sulfamine, or trilonate, or dicyano-argentate or cyanide electrolyte with a marking phosphor coated with a protective shell in the form of a protective capsule inert with respect to the electrolyte, and the subsequent implementation of brand overgrowth uyuschego phosphor coated during the deposition of the metal coating, wherein the protective sheath is made of optically and / or physically transparent, with the ability to skip waves which are in the optically visible and / or invisible spectrum.
  • the process is carried out with continuous stirring of the electrolyte at a speed of up to 650 rpm, and the deposition is carried out at an electrolyte temperature of 20-70 ° C and current density required for the process.
  • aluminum oxide or titanium oxide is applied, deposited in vacuum using the ALD process - atomic layer deposition.
  • Silicon oxide is applied as a protective sheath, deposited in vacuum using the CVD process - chemical vapor deposition.
  • a protective shell calcium silicate treated with zinc sulfate is used.
  • An electroluminophore and / or Stokes phosphor and / or anti-Stokes phosphor are used as the marking phosphor.
  • nickel or copper, or brass, or silver are used, of which the anodes are made, respectively.
  • a multilayer valuable product such as a token, medal, coin, badge, is obtained by the method as described above.
  • Example 1 The invention is illustrated by examples.
  • Example 1 The invention is illustrated by examples.
  • Example 1 The invention is illustrated by examples.
  • a Watts type sulfate electrolyte consisting of divalent nickel sulfate, divalent nickel chloride and boric acid is poured.
  • a token from, for example, an iron alloy is immersed with the help of rod holders in a bath for applying a galvanic metal coating of nickel, equipped with anodes of chemically pure nickel, into which a sulfate electrolyte with a marking phosphor is poured (inorganic chemical compound, for example, Y 2 0 2 S: Yb, Er; Y 2 0 2 S: Tb; n8: Cu-electroluminophore), coated in the form a protective capsule that is inert with respect to the electrolyte, and the surface is “overgrown” with continuous stirring of the electrolyte at a speed of 650 rpm, and the deposition is carried out at an electrolyte temperature of 70 ° C and current density necessary for the process.
  • alumina is applied optically and / or physically transparent, with the ability to transmit waves in the optically visible and / or invisible spectrum (in another example, titanium oxide) in vacuum using the ALD process (ASO - atomic layer deposition).
  • an electroluminophore and / or Stokes phosphor and / or anti-Stokes phosphor for example, ZnS: Cu-electroluminophore; Y 2 0 2 S: Yb, Er; Y 2 0 2 S: Tb) were used.
  • a marking phosphor inorganic chemical compound, for example, Y 2 0 2 S: Yb, Er; Y 2 0 2 S: Tb; ZnS: Cu
  • silicon oxide in vacuum is applied as a protective sheath using the CVD process - chemical vapor deposition.
  • an electroluminophore and / or Stokes phosphor and / or anti-Stokes phosphor an inorganic chemical compound, for example, Y 2 0 2 S: Yb, Er; Y 2 0 2 S: Tb; ZnS: Cu electroluminophore, were used.
  • An icon made of, for example, an iron alloy, is immersed with the help of rod holders in a bath for applying an electroplated metal coating of brass, equipped with anodes of chemically pure copper and zinc, into which an electrolyte for applying brass is either filled, or sulfate, or cyanide, or pyrophosphate with a marking phosphor (inorganic chemical a compound, for example, Y 2 0 2 S: Yb, Er; Y 2 0 2 S: Tb; ZnS: Cu-electroluminophore), coated in the form of a protective capsule, inert with respect to the electrolyte, and the surface is “overgrown” with continuous mixing of the electrolyte at a speed of 214 rpm, and deposition is carried out at an electrolyte temperature of 50 ° C and current density required to carry out the process.
  • a marking phosphor inorganic chemical a compound, for example, Y 2 0 2 S: Yb, Er; Y 2
  • calcium silicate treated with zinc sulfate is used as a protective sheath.
  • an electroluminophore and / or a Stokes phosphor and / or an anti-Stokes phosphor was used — an inorganic chemical compound, for example, Y 2 0 2 S: Yb, Er; Y 2 0 2 S: Tb; ZnS: Cu electroluminophore).
  • the medal is immersed with the help of holders in a bath for applying a galvanic metal coating of silver, equipped with anodes of chemically pure silver, into which a sulfate electrolyte for applying silver is added, or sulfate, or cyanide, or pyrophosphate with a marking phosphor (inorganic chemical compound, for example, Y 2 0 2 S: Yb, Er; Y 2 0 2 S: Tb; ZnS: Cu-electroluminophore), coated in the form of a protective capsule, inert with respect to the electrolyte, and the surface is “overgrown” with continuous mixing of the electrolyte at a speed of 430 rpm, and deposition is carried out at an electrolyte temperature of 50 ° C and current density required to carry out the process.
  • a marking phosphor inorganic chemical compound, for example, Y 2 0 2 S: Yb, Er; Y 2 0 2 S: Tb; ZnS
  • calcium silicate treated with zinc sulfate is used as a protective sheath.
  • metal coatings were obtained with embedded encapsulated phosphors located along the thickness of the coating giving a response to the introduced excitation.
  • the invention is applicable in the manufacture of multilayer products containing metal and protective layers for protection against counterfeiting, in particular, in the production of multilayer, made of different materials, metal products protected from forgery, such as for example, exchange or collection of prefabricated coins, metal tokens, medals, and offers an original and high-precision method for their manufacture.

Abstract

The invention is used for the counterfeit protection of multi-layered valuable items, such as coins, metal tokens and medals. A multi-layered valuable item with a fluorescent-type security element is produced by means of a method which includes immersing an item, with the aid of a clamping rod, into a bath for the application of a galvanic metal coating, wherein the bath is provided with anodes made of a chemically pure metal and is filled with a pyrophosphate or sulphate or ferricyanide or polyphosphate or thiocyanate or iodide or sulphamic or trilonate or dicyanoargentate or cyanide electrolyte with a marking fluorescent substance which is covered with a protective shell in the form of a protective capsule that is inert to the electrolyte, and subsequently building up the marking fluorescent substance in the shell as the metal coating is deposited. The protective shell is optically and/or physically transparent and is adapted to allow waves in the visible and/or invisible spectrum to pass, and the process is carried out under constant agitation of the electrolyte.

Description

СПОСОБ ИЗГОТОВЛЕНИЯ многослойного ЦЕННОГО ИЗДЕЛИЯ С ЗАЩИТНЫМ ЭЛЕМЕНТОМ ЛЮМИНЕСЦЕНТНОГО ТИПА И МНОГОСЛОЙНОЕ METHOD FOR PRODUCING A LAYERED VALUABLE PRODUCT WITH A PROTECTIVE ELEMENT OF A LUMINESCENT TYPE AND MULTILAYERED
ЦЕННОЕ ИЗДЕЛИЕ VALUABLE PRODUCT
Область техники Technical field
Изобретение относится к многослойным изделиям, содержащим металлические и защитный слои для защиты от подделки, в частности, к производству многослойных, выполненных из разных материалов металлических изделий, защищенных от подделки, таких как, например, разменных или коллекционных сборных монет, металлических жетонов, медалей, а также - к оригинальному и высокоточному способу их изготовления.  The invention relates to multilayer products containing metal and protective layers for protection against counterfeiting, in particular, to the production of multilayer metal products made of different materials, protected from counterfeiting, such as, for example, exchange or collection precast coins, metal tokens, medals, as well as to the original and high-precision method of their manufacture.
Предшествующий уровень техникиState of the art
Из уровня техники известно многослойное монетовидное изделие, в частности, жетон, содержащий кодирующие элементы в виде слоя люминесцентного вещества RU 2121285 С1. Кодирующие элементы в данном изделии обеспечивают повышение степени защищенности от подделки. A multilayer coin-like product is known from the prior art, in particular, a token containing coding elements in the form of a layer of a luminescent substance RU 2121285 C1. Coding elements in this product provide an increase in the degree of protection against counterfeiting.
Известно также многослойное изделие, содержащее, по меньшей мере, один металлический и/или полимерный слой основы и дополнительный слой с кодирующими элементами, отличающееся тем, что дополнительный слой выполнен в виде слоя красящего вещества, который образует двухмерный QR- код и размещен на поверхности многослойного изделия (RU 134483, В32В 15/04 2013). Also known is a multilayer product containing at least one metal and / or polymer base layer and an additional layer with coding elements, characterized in that the additional layer is made in the form a layer of a coloring matter that forms a two-dimensional QR code and is placed on the surface of the multilayer product (RU 134483, B32B 15/04 2013).
Известен также способ получения двухслойного защитного покрытия, в котором на поверхность изделия гальваническим методом сначала наносят никелевое покрытие толщиной 5-7 мкм, затем медное, толщиной 20-25 мкм, а затем проводят термообработку в три этапа (RU 2066715, В32В 15/00, 1994), который является ближайшим аналогом заявленного способа.  There is also a method for producing a two-layer protective coating, in which the nickel coating is 5-7 μm thick, then copper, 20-25 μm thick, and then heat treatment is carried out in three stages (RU 2066715, B32B 15/00, 1994), which is the closest analogue of the claimed method.
Наиболее близким к заявленному изделию является многослойное металлическое изделие, содержащее металл, выбранный из ряда алюминий, титан, тантал, ниобий, с верхним поверхностным слоем, подвергнутым электрохимической обработке (RU 99379 В32В 15/00, 2010).  Closest to the claimed product is a multilayer metal product containing a metal selected from the range of aluminum, titanium, tantalum, niobium, with the upper surface layer subjected to electrochemical processing (RU 99379 B32B 15/00, 2010).
Недостатком является низкая степень защищенности, который устраняется в заявленном изобретении за счет использования заключенного в прозрачную оболочку люминофора, который нанесен при гальванизации изделия.  The disadvantage is the low degree of security, which is eliminated in the claimed invention through the use of a phosphor enclosed in a transparent shell, which is deposited during galvanization of the product.
Раскрытие изобретения Disclosure of invention
Технический результат - повышение степени защищенности, достигается тем, что способ изготовления многослойного ценного изделия с защитным элементом люминесцентного типа, включающий погружение изделия с помощью штанг-держателей в ванну для нанесения гальванического металлического покрытия, снабженную анодами из металла, необходимого для проведения процесса осаждения, в которую залит или пирофосфатный, или сульфатный, или железосинеродистый, или полифосфатный, или роданистый, или йодистый, или сульфаминовый, или трилонатный, или дицианоаргентатный, или цианистый электролит с маркирующим люминофором, покрытым защитной оболочкой в виде защитной капсулы, инертной по отношению к электролиту, и последующее осуществление заращивания маркирующего люминофора в оболочке в процессе осаждения металлического покрытия, при этом защитная оболочка выполнена оптически и/или физически прозрачной, с возможностью пропускать волны, находящиеся в оптически видимом и/или невидимом спектре. The technical result is an increase in the degree of security, achieved by the fact that the method of manufacturing a multilayer valuable product with a protective element of a luminescent type, including immersing the product with using rod holders in a bath for plating a metal coating, equipped with anodes of the metal necessary for the deposition process, into which it is either pyrophosphate, or sulfate, or iron-hydrogen, or polyphosphate, or rhodanic, or iodide, or sulfamine, or trilonate, or dicyano-argentate or cyanide electrolyte with a marking phosphor coated with a protective shell in the form of a protective capsule inert with respect to the electrolyte, and the subsequent implementation of brand overgrowth uyuschego phosphor coated during the deposition of the metal coating, wherein the protective sheath is made of optically and / or physically transparent, with the ability to skip waves which are in the optically visible and / or invisible spectrum.
Процесс ведут при непрерывном перемешивании электролита со скоростью до 650 об/мин, а осаждение ведут при температуре электролита 20-70°С и плотности тока, необходимой для проведения процесса.  The process is carried out with continuous stirring of the electrolyte at a speed of up to 650 rpm, and the deposition is carried out at an electrolyte temperature of 20-70 ° C and current density required for the process.
В качестве защитной оболочки применяют оксид алюминия или оксид титана, нанесенный в вакууме с помощью процесса ALD - атомнослоевого осаждения.  As a protective shell, aluminum oxide or titanium oxide is applied, deposited in vacuum using the ALD process - atomic layer deposition.
В качестве защитной оболочки применяют оксид кремния, нанесенный в вакууме с помощью процесса CVD - химического парофазного осаждения. В качестве защитной оболочки используют силикат кальция, обработанный сульфатом цинка. Silicon oxide is applied as a protective sheath, deposited in vacuum using the CVD process - chemical vapor deposition. As a protective shell, calcium silicate treated with zinc sulfate is used.
В качестве маркирующего люминофора используют электролюминофор и/или стоксовый люминофор, и/или антистоксовый люминофор.  An electroluminophore and / or Stokes phosphor and / or anti-Stokes phosphor are used as the marking phosphor.
В качестве металлического покрытия используют никель или медь, или латунь, или серебро, из которых выполнены аноды, соответственно.  As a metal coating, nickel or copper, or brass, or silver are used, of which the anodes are made, respectively.
Многослойное ценное изделие, такое как жетон, медаль, монета, значок, получено способом как описано выше.  A multilayer valuable product, such as a token, medal, coin, badge, is obtained by the method as described above.
Лучший пример осуществления изобретения The best example of carrying out the invention
Сущность изобретения поясняется примерами. Пример 1.  The invention is illustrated by examples. Example 1
В ванну заливают, например, сульфатный электролит типа Уоттса, состоящий из двухвалентного сульфата никеля, двухвалентного хлористого никеля и кислоты борной. Жетон из, например, сплава железа, погружают с помощью штанг- держателей в ванну для нанесения гальванического металлического покрытия из никеля, снабженную анодами из химически чистого никеля, в которую залит сульфатный электролит с маркирующим люминофором (неорганическое химическое соединение, например, Y202S:Yb,Er; Y202S:Tb; п8:Си-электролюминофор), покрытым оболочкой в виде защитной капсулы, инертной по отношению к электролиту, и «заращивают» поверхность при непрерывном перемешивании электролита со скоростью 650 об/мин, а осаждение ведут при температуре электролита 70°С и плотности тока, необходимой для проведения процесса. In the bath, for example, a Watts type sulfate electrolyte consisting of divalent nickel sulfate, divalent nickel chloride and boric acid is poured. A token from, for example, an iron alloy, is immersed with the help of rod holders in a bath for applying a galvanic metal coating of nickel, equipped with anodes of chemically pure nickel, into which a sulfate electrolyte with a marking phosphor is poured (inorganic chemical compound, for example, Y 2 0 2 S: Yb, Er; Y 2 0 2 S: Tb; n8: Cu-electroluminophore), coated in the form a protective capsule that is inert with respect to the electrolyte, and the surface is “overgrown” with continuous stirring of the electrolyte at a speed of 650 rpm, and the deposition is carried out at an electrolyte temperature of 70 ° C and current density necessary for the process.
В качестве защитной оболочки наносят оксид алюминия оптически и/или физически прозрачный, с возможностью пропускать волны, находящиеся в оптически видимом и/или невидимом спектре, (в другом примере - оксид титана) в вакууме с помощью процесса ALD (АСО - атомнослоевого осаждения).  As a protective sheath, alumina is applied optically and / or physically transparent, with the ability to transmit waves in the optically visible and / or invisible spectrum (in another example, titanium oxide) in vacuum using the ALD process (ASO - atomic layer deposition).
(В различных примерах использовали электролюминофор и/или стоксовый люминофор, и/или антистоксовый люминофор, например, ZnS:Cu- электролюминофор; Y202S:Yb,Er; Y202S:Tb). (In various examples, an electroluminophore and / or Stokes phosphor and / or anti-Stokes phosphor, for example, ZnS: Cu-electroluminophore; Y 2 0 2 S: Yb, Er; Y 2 0 2 S: Tb) were used.
Пример 2. Example 2
Жетон из, например, сплава железа, погружают с помощью штанг-держателей в ванну для нанесения гальванического металлического покрытия из меди, снабженную анодами из химически чистой меди, в которую залит электролит для нанесения меди или сульфатный, или цианистый, или пирофосфатный с маркирующим люминофором (неорганическое химическое соединение, например, Y202S:Yb,Er; Y202S:Tb; ZnS:Cu- электролюминофор), покрытым оболочкой в виде защитной капсулы, инертной по отношению к электролиту, и «заращивают» поверхность при непрерывном перемешивании электролита со скоростью 650 об/мин, а осаждение ведут при температуре электролита 40°С и плотности тока, необходимой для проведения процесса. A token from, for example, an iron alloy, is immersed with the help of rod holders in a bath for applying a galvanic metal coating of copper, equipped with anodes of chemically pure copper, into which the electrolyte for depositing copper is either sulphate, or cyanide, or pyrophosphate with a marking phosphor ( inorganic chemical compound, for example, Y 2 0 2 S: Yb, Er; Y 2 0 2 S: Tb; ZnS: Cu- electroluminophore), coated in the form of a protective capsule, inert with respect to the electrolyte, and the surface is “overgrown” with continuous stirring of the electrolyte at a speed of 650 rpm, and the deposition is carried out at an electrolyte temperature of 40 ° C and current density required for the process.
В качестве защитной оболочки наносят оптически и/или физически прозрачный, с возможностью пропускать волны, находящиеся в оптически видимом и/или невидимом спектре, оксид кремния в вакууме с помощью процесса CVD - химического парофазного осаждения.  Optically and / or physically transparent, with the ability to transmit waves in the optically visible and / or invisible spectrum, silicon oxide in vacuum is applied as a protective sheath using the CVD process - chemical vapor deposition.
(В различных примерах использовали электролюминофор и/или стоксовый люминофор, и/или антистоксовый люминофор - неорганическое химическое соединение, например- Y202S:Yb,Er; Y202S:Tb; ZnS:Cu- электролюминофор). (In various examples, an electroluminophore and / or Stokes phosphor and / or anti-Stokes phosphor, an inorganic chemical compound, for example, Y 2 0 2 S: Yb, Er; Y 2 0 2 S: Tb; ZnS: Cu electroluminophore, were used.
Пример 3. Example 3
Значок из, например, сплава железа, погружают с помощью штанг-держателей в ванну для нанесения гальванического металлического покрытия из латуни, снабженную анодами из химически чистой меди и цинка, в которую залит электролит для нанесения латуни или сульфатный, или цианистый, или пирофосфатный с маркирующим люминофором (неорганическое химическое соединение, например - Y202S:Yb,Er; Y202S:Tb; ZnS:Cu- электролюминофор), покрытым оболочкой в виде защитной капсулы, инертной по отношению к электролиту, и «заращивают» поверхность при непрерывном перемешивании электролита со скоростью 214 об/мин, а осаждение ведут при температуре электролита 50°С и плотности тока, необходимой для проведения процесса. An icon made of, for example, an iron alloy, is immersed with the help of rod holders in a bath for applying an electroplated metal coating of brass, equipped with anodes of chemically pure copper and zinc, into which an electrolyte for applying brass is either filled, or sulfate, or cyanide, or pyrophosphate with a marking phosphor (inorganic chemical a compound, for example, Y 2 0 2 S: Yb, Er; Y 2 0 2 S: Tb; ZnS: Cu-electroluminophore), coated in the form of a protective capsule, inert with respect to the electrolyte, and the surface is “overgrown” with continuous mixing of the electrolyte at a speed of 214 rpm, and deposition is carried out at an electrolyte temperature of 50 ° C and current density required to carry out the process.
В качестве защитной оболочки используют оптически и/или физически прозрачный, с возможностью пропускать волны, находящиеся в оптически видимом и/или невидимом спектре, силикат кальция, обработанный сульфатом цинка.  Optically and / or physically transparent, with the ability to transmit waves in the optically visible and / or invisible spectrum, calcium silicate treated with zinc sulfate is used as a protective sheath.
(В различных примерах использовали электролюминофор и/или стоксовый люминофор и/или антистоксовый люминофор - не органическое химическое соединение, например - Y202S:Yb,Er; Y202S:Tb; ZnS:Cu- электролюминофор). (In various examples, an electroluminophore and / or a Stokes phosphor and / or an anti-Stokes phosphor was used — an inorganic chemical compound, for example, Y 2 0 2 S: Yb, Er; Y 2 0 2 S: Tb; ZnS: Cu electroluminophore).
Пример 4. Example 4
Как в примере 3, медаль погружают с помощью штанг- держателей в ванну для нанесения гальванического металлического покрытия из серебра, снабженную анодами из химически чистого серебра, в которую залит сульфатный электролит для нанесения серебра или сульфатный, или цианистый, или пирофосфатный с маркирующим люминофором (неорганическое химическое соединение, например, Y202S:Yb,Er; Y202S:Tb; ZnS:Cu- электролюминофор), покрытым оболочкой в виде защитной капсулы, инертной по отношению к электролиту, и «заращивают» поверхность при непрерывном перемешивании электролита со скоростью 430 об/мин, а осаждение ведут при температуре электролита 50°С и плотности тока, необходимой для проведения процесса. As in example 3, the medal is immersed with the help of holders in a bath for applying a galvanic metal coating of silver, equipped with anodes of chemically pure silver, into which a sulfate electrolyte for applying silver is added, or sulfate, or cyanide, or pyrophosphate with a marking phosphor (inorganic chemical compound, for example, Y 2 0 2 S: Yb, Er; Y 2 0 2 S: Tb; ZnS: Cu-electroluminophore), coated in the form of a protective capsule, inert with respect to the electrolyte, and the surface is “overgrown” with continuous mixing of the electrolyte at a speed of 430 rpm, and deposition is carried out at an electrolyte temperature of 50 ° C and current density required to carry out the process.
В качестве защитной оболочки используют оптически и/или физически прозрачный, с возможностью пропускать волны, находящиеся в оптически видимом и/или невидимом спектре, силикат кальция, обработанный сульфатом цинка.  Optically and / or physically transparent, with the ability to transmit waves in the optically visible and / or invisible spectrum, calcium silicate treated with zinc sulfate is used as a protective sheath.
Во всех примерах получили металлические покрытия с заращенными капсулированными люминофорами, расположенными по толщине покрытия, дающими отклик на привносимое возбуждение. In all examples, metal coatings were obtained with embedded encapsulated phosphors located along the thickness of the coating giving a response to the introduced excitation.
Таким образом, технический результат наглядно достигнут заявленным изобретением. Промышленная применимость  Thus, the technical result is clearly achieved by the claimed invention. Industrial applicability
Изобретение применимо при производстве многослойных изделий, содержащих металлические и защитный слои для защиты от подделки, в частности, при производстве многослойных, выполненных из разных материалов, металлических изделий, защищенных от подделки, таких как, например, разменных или коллекционных сборных монет, металлических жетонов, медалей, и предлагает оригинальный и высокоточный способ их изготовления. The invention is applicable in the manufacture of multilayer products containing metal and protective layers for protection against counterfeiting, in particular, in the production of multilayer, made of different materials, metal products protected from forgery, such as for example, exchange or collection of prefabricated coins, metal tokens, medals, and offers an original and high-precision method for their manufacture.

Claims

ФОРМУЛА ИЗОБРЕТЕНИЯ CLAIM
1. Способ изготовления многослойного ценного изделия с защитным элементом люминесцентного типа, включающий погружение изделия с помощью штанг- держателей в ванну для нанесения гальванического металлического покрытия, снабженную анодами из химически чистого металла, в которую залит или пирофосфатный, или сульфатный, или железосинеродистый, или полифосфатный, или роданистый, или йодистый, или сульфаминовый, или трилонатный, или дицианоаргентатный, или цианистый электролит с маркирующим люминофором, покрытым защитной оболочкой в виде защитной капсулы, инертной по отношению к электролиту, и последующее осуществление заращивания маркирующего люминофора в оболочке в процессе осаждения металлического покрытия, при этом защитная оболочка выполнена оптически и/или физически прозрачной, с возможностью пропускать волны, находящиеся в оптически видимом и/или невидимом спектре. 1. A method of manufacturing a multilayer valuable product with a protective element of a luminescent type, comprising immersing the product with the help of rod holders in a bath for applying a galvanic metal coating, equipped with anodes of chemically pure metal, into which it is either pyrophosphate, or sulfate, or iron-sulfide, or polyphosphate or thiocyanate, or iodide, or sulfamic, or trilonate, or dicyano-argentate, or cyanide electrolyte with a marking phosphor coated with a protective shell in the form of itnoy capsules, inert to the electrolyte, and the subsequent implementation overgrowth marking phosphor coated during the deposition of the metal coating, wherein the protective sheath is made of optically and / or physically transparent, with the ability to skip waves which are in the optically visible and / or invisible spectrum.
2. Способ по п.1, отличающийся тем, что процесс ведут при непрерывном перемешивании электролита со скоростью до 650 об/мин, а осаждение ведут при температуре электролита 20-70°С и плотности тока, необходимой для проведения процесса. 2. The method according to claim 1, characterized in that the process is carried out with continuous stirring of the electrolyte at a speed of up to 650 rpm, and the deposition is carried out at an electrolyte temperature of 20-70 ° C and current density necessary for the process.
3. Способ по п.1 , отличающийся тем, что в качестве защитной оболочки наносят оксид алюминия или оксид титана в вакууме с помощью процесса ALD - атомнослоевого осаждения. 3. The method according to claim 1, characterized in that alumina or titanium oxide is applied in a vacuum as a protective sheath using the ALD atom-layer deposition process.
5 4. Способ по п.1, отличающийся тем, что в качестве защитной оболочки наносят оксид кремния в вакууме с помощью процесса CVD - химического парофазного осаждения .  5 4. The method according to claim 1, characterized in that silicon dioxide is applied in a vacuum as a protective sheath using the CVD process - chemical vapor deposition.
5. Способ по п.1 , отличающийся тем, что в качестве защитной оболочки используют силикат кальция, обработанный ю сульфатом цинка.  5. The method according to claim 1, characterized in that the calcium silicate treated with zinc sulfate is used as a protective sheath.
6. Способ по п.1, отличающийся тем, что в качестве маркирующего люминофора используют электролюминофор и/или стоксовый люминофор и/или антистоксовый люминофор.  6. The method according to claim 1, characterized in that the electroluminophore and / or Stokes phosphor and / or anti-Stokes phosphor are used as the marking phosphor.
15 7. Способ по п.1, отличающийся тем, что в качестве металлического покрытия используют никель или медь, или латунь, или серебро, из которых выполнены аноды, соответственно.  15 7. The method according to claim 1, characterized in that nickel or copper, or brass, or silver, of which anodes are made, are used as a metal coating.
8. Многослойное ценное изделие, такое как жетон, медаль, 20 монета, значок, полученное способом по любому из пунктов 1-7.  8. A multilayer valuable product, such as a badge, medal, 20 coin, badge, obtained by the method according to any one of paragraphs 1-7.
PCT/RU2016/000758 2015-11-25 2016-11-09 Method of manufacturing a multi-layered valuable item with a fluorescent-type security element and multi-layered valuable item WO2017091106A1 (en)

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