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WO2009043948A1 - Procédé de conditionnement de matières minérales telles que des additifs de sécurité - Google Patents

Procédé de conditionnement de matières minérales telles que des additifs de sécurité Download PDF

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Publication number
WO2009043948A1
WO2009043948A1 PCT/ES2008/000602 ES2008000602W WO2009043948A1 WO 2009043948 A1 WO2009043948 A1 WO 2009043948A1 ES 2008000602 W ES2008000602 W ES 2008000602W WO 2009043948 A1 WO2009043948 A1 WO 2009043948A1
Authority
WO
WIPO (PCT)
Prior art keywords
inorganic material
paper
grinding
carried out
conditioned
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/ES2008/000602
Other languages
English (en)
Spanish (es)
Inventor
Antonio Olmos Ruiz
Jose Mendia Aguilar
Javier Baraja Carracedo
Juan Antonio Rubio Sanz
Miguel Angel Rodriguez Barbero
Jose Francisco Fernandez Lozano
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fabrica Nacional de Moneda y Timbre
Original Assignee
Fabrica Nacional de Moneda y Timbre
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fabrica Nacional de Moneda y Timbre filed Critical Fabrica Nacional de Moneda y Timbre
Publication of WO2009043948A1 publication Critical patent/WO2009043948A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D15/00—Printed matter of special format or style not otherwise provided for
    • 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
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7701—Chalogenides
    • C09K11/7703—Chalogenides with alkaline earth metals
    • 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
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7774—Aluminates
    • 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
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D21H21/44—Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
    • G—PHYSICS
    • G07—CHECKING-DEVICES
    • G07D—HANDLING OF COINS OR VALUABLE PAPERS, e.g. TESTING, SORTING BY DENOMINATIONS, COUNTING, DISPENSING, CHANGING OR DEPOSITING
    • G07D7/00—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency

Definitions

  • the invention belongs to the field of inorganic materials used as security elements in paper. More specifically, the invention relates to a method for conditioning said inorganic materials as safety additives, as well as to the inorganic conditioned material thus obtained, to a safety paper comprising said inorganic material conditioned in its composition and to the use of the material inorganic conditioning for the manufacture of security paper.
  • the operative form in the preparation of the products is always the same: once the physical property to be developed in the document is known, the raw material is defined with the appropriate additives or dopants to design the response of so that it stays in a desired range, whether of frequencies, electric field, magnetic permeability, etc.
  • the active material obtained by synthesis, whose properties of evaluable behavior are known, it is necessary to process it to achieve the precise characteristics to be able to add it to the paper.
  • US 6344261 describes a series of inorganic materials with luminescent capacity useful as safety elements.
  • the patent also describes the preparation of said materials which, after their synthesis, are incorporated directly into the paper pulp.
  • the direct incorporation of the powdered materials into the paper pulp results in an insufficient dispersion of the material in the paper that is desirable to improve.
  • the inventors of the present invention have developed a method for conditioning inorganic materials for incorporation into paper pastes This is based both on the use of suitable average particle sizes and on the prior dispersion of said particles in a conditioning solution.
  • the method of the present invention allows to obtain clearly improved and more homogeneous dispersions of the inorganic safety material in the paper pulp and therefore higher quality security papers.
  • the invention relates to a method for the conditioning of applicable inorganic materials as safety additives in paper comprising: a) Calcination and agglomeration of the inorganic material at a temperature of up to 1600 ° C,
  • inorganic material is any mineral substance commonly used as a paper safety additive. Normally these minerals have some physical property that allows them to act as such security elements. Inorganic materials used as safety elements are normally capable of being excited at certain wavelengths while emitting luminescence to different lengths.
  • the inorganic materials of the invention are minerals that comprise rare earths since these have the ability to excite in the visible spectral region and have a high level of emission intensity in the near-infrared spectral region.
  • the inorganic materials of the invention have a perovskite-like structure such as strontium titanate doped with praseodymium or other rare earths.
  • the inorganic material has a garnet-like structure such as ytrium aluminate doped with erbium or other rare earths.
  • the calcination and agglomeration of the inorganic material previously synthesized is carried out.
  • This heat treatment serves to improve certain aspects of the synthesized products such as their chemical stability, degree of crystallinity, their crystallite size and their state of agglomeration.
  • the treatment must be designed according to the material and synthesis method by which it has been synthesized although in general the calcination will be carried out at a temperature not exceeding 1600 0 C. In a preferred embodiment of the invention the calcination will be carried out between 800 and 1300 0 C.
  • the second stage of the process involves subjecting the agglomerated material to one or several grinding stages up to an average particle size within the range of 2 to 20 ⁇ m. These are sizes compatible with the paper preparation. On the one hand the particles cannot be greater than 20 ⁇ m so that they are perfectly integrated in the thickness of the sheet of the final paper and to avoid its location and identification because it is a security element. On the other hand, if the concentration of particles less than 2 ⁇ m is very high, the effectiveness of the product will be low since during the papermaking process, much of the material will be lost with the water. Therefore, the size ranges must be in a
  • the average particle size must be within the range of 3 to 7 ⁇ m.
  • the materials are densified, so that before the fine grinding until reaching the desired particle size, it is necessary to start with a previous or broken grinding, which can be carried out by techniques such as breaking the jaws, hammers or of roller. These types of treatments are done dry. In the case of soft agglomerates, high shear agitation systems can be used, taking advantage of this stage for the suspension of the material.
  • the last step of the method comprises the suspension of the material with the appropriate particle size in water in the presence of one or more dispersing agents.
  • the amount of dispersant must be determined according to the unit of active material to be processed. As a reference unit, the material surface that is the one that makes rheological sense should be used. Therefore, the amount of dispersing agent necessary for the suspension will depend on the specific surface area of the final product.
  • organic and inorganic dispersants are valid for the purposes of the present invention. As for the predominant dispersing effect, this may be steric in the case of ammonium or ionic polyacrylate, as in the case of sodium or mixed hexametaphosphate, such as in the case of polyethylene glycol. Both ammonium polyacrylate, such as sodium hexametaphosphate and polyethylene glycol represent the preferred dispersants of the invention although other dispersants may also be valid. Dispersants can be used individually or mixed together.
  • the method of the invention may include several optional steps depending on the type of material to be processed and the use that is intended to be given to the final conditioning solution.
  • the material to be agglomerated when it has the appropriate dimensions for calcination, it can be subjected to some previous grinding stage. This grinding can be performed by any of the techniques mentioned above.
  • the circumstance can be given that the conditioned material will be used immediately for the preparation of the paper, so that there would be no problem.
  • the application of the material is to be carried out later and the material must be stored or transported, it can be subjected to a drying stage to remove the water.
  • This drying stage can be carried out by means of a press filter or spray. This last technique is preferable.
  • Another aspect of the invention relates to the conditioned inorganic material obtainable according to the method of the invention.
  • the object of the invention is also a security paper comprising an inorganic conditioned material obtainable according to the method of
  • a final aspect of the invention refers to the use of a conditioned inorganic material according to the method of the invention in the preparation of security paper.
  • a luminescent active substance with a Perovskite-like structure consisting of Strontium titanate doped with Praseodymium, prepared as described in the work of H. Yamamoto, S. Okamoto and H. Kobayashi (Journal of Luminescence 100 (2002) 325-332).
  • the appropriate quantities of SrCO 3 , TiO 2 and PrCI 3 are homogenized in a dry ball mill and placed in a Cordierita-mullita crucible of low form and of 2 liters capacity.
  • Said crucible is introduced in an electric oven capable of reaching 1500 0 C. It is heated at a speed of 2 ° C / min to 800 0 C to achieve the decomposition of raw materials and subsequently the temperature is raised to 1300 0 C at a speed of 3 ° C / min. It is kept at said temperature for 120 min and cooled at a speed of 3 ° C / min. At 200 ° C the oven opens to accelerate cooling.
  • the obtained agglomerated powder is subjected to a previous grinding by means of a jaw crusher to a smaller size 0.5 mm
  • the powder thus obtained will be broken down into a continuous high shear agitation equipment, of the IKA brand.
  • a mixture consisting of 49.9% by weight of deionized water, 50% by weight of the substance to be deagglomerated and 0.1% of sodium hexametaphosphate is prepared.
  • Said mixture will be processed with the high shear agitator through the system of successive passes to ensure that all the material passes through the deagglomeration chamber. The passes continue until the particle size of the suspension, determined by dispersion of laser radiation indicates that 100% of the population is below 20 micrometers, and the average size between 2 and 7 micrometers, sizes compatible with the manufacture of paper.
  • the suspension thus obtained can be added to the formulation of the corresponding paper pulp.
  • a luminescent active substance with a garnet structure consisting of Ytrium aluminate doped with Erbium, prepared as described in the work of A. Leleckaite and A. Kareiva (Optical Materials 26 (2004) 123- 128). Suitable amounts of Y 2 O 3 , Er 2 O 3 and AI (NO 3 ) 3 .9H 2 O are processed as described below.
  • the Ytrium oxide is dissolved in a 0.2 molar solution of acetic acid at 65 0 C. To this solution is added Erbium oxide dissolved in acetic acid. Next, the Aluminum Nitrate, previously dissolved in water, is added. The whole is stirred for 3 hours at 65 0 C.
  • 1,2-ethanediol is added as a complexing agent.
  • the solution is concentrated by slow evaporation at 65 0 C until it becomes a transparent gel.
  • the gel is mechanically crushed and introduced into a Cordierita-mullita crucible of low shape and 2 liters capacity.
  • Said crucible is introduced in an electric oven capable of reaching 1500 0 C. It is heated at a speed of 2 ° C / min to 800 0 C where 120 min is maintained to achieve the decomposition and reaction of the raw materials.
  • the agglomerate thus obtained is subjected to a previous grinding by means of a jaw crusher up to a size smaller than 0.5 mm.
  • the obtained agglomerated powder is subjected to a previous grinding by means of a jaw crusher up to a size smaller than 0.5 mm.
  • the powder thus obtained will be broken down into a continuous high shear agitation equipment, of the IKA brand.
  • a mixture consisting of 54.7% by weight of deionized water, 45% by weight of the substance to be deagglomerated is prepared and 0.3% ammonium polyacrylate is added (Dolapix CE64 Zschimmer & Schwarz GMBH & Co KG) Said mixture will be processed with the high shear agitator through the system of successive passes to ensure that all the material passes through the breakdown chamber. The passes continue until the particle size of the suspension, determined by means of laser radiation dispersion, indicates that 90% of the population is below 100 micrometers.
  • the suspension is introduced into an attrition mill with zirconium oxide balls of 3 mm and thus processed to reach an average size between 3 and 7 micrometers, sizes compatible with papermaking.
  • the suspension thus obtained can be added to the formulation of the corresponding paper pulp.
  • an impeller atomizer is used, using an air pressure of 6 Kgr / cm 2 to move the impeller, an inlet air temperature of 35O 0 C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Paper (AREA)

Abstract

L'invention concerne un procédé de conditionnement de matières inorganiques telles que des additifs de sécurité, ainsi que la matière conditionnée ainsi obtenue, un papier de sécurité dont la composition comprend cette matière inorganique conditionnée, et l'utilisation de ladite matière inorganique conditionnée pour la fabrication d'un papier de sécurité.
PCT/ES2008/000602 2007-10-04 2008-09-24 Procédé de conditionnement de matières minérales telles que des additifs de sécurité Ceased WO2009043948A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ESP200702610 2007-10-04
ES200702610A ES2317790B1 (es) 2007-10-04 2007-10-04 Metodo de acondicionamiento de materiales minerales como aditivos de seguridad.

Publications (1)

Publication Number Publication Date
WO2009043948A1 true WO2009043948A1 (fr) 2009-04-09

Family

ID=40513488

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/ES2008/000602 Ceased WO2009043948A1 (fr) 2007-10-04 2008-09-24 Procédé de conditionnement de matières minérales telles que des additifs de sécurité

Country Status (2)

Country Link
ES (1) ES2317790B1 (fr)
WO (1) WO2009043948A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6200628B1 (en) * 1997-12-29 2001-03-13 Sicpa Holding S.A. Use of inorganic particles and method for making and identifying a substrate or an article
US6344261B1 (en) * 1998-02-02 2002-02-05 Giesecke & Devrient Gmbh Printed document having a value and comprising a luminescent authenticity feature based on a host lattice

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6200628B1 (en) * 1997-12-29 2001-03-13 Sicpa Holding S.A. Use of inorganic particles and method for making and identifying a substrate or an article
US6344261B1 (en) * 1998-02-02 2002-02-05 Giesecke & Devrient Gmbh Printed document having a value and comprising a luminescent authenticity feature based on a host lattice

Also Published As

Publication number Publication date
ES2317790B1 (es) 2010-02-16
ES2317790A1 (es) 2009-04-16

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