EP3178659B1 - Method for preparing paper having transparent portions, and paper having transparent portions prepared using said method - Google Patents

Method for preparing paper having transparent portions, and paper having transparent portions prepared using said method Download PDF

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Publication number
EP3178659B1
EP3178659B1 EP15829700.2A EP15829700A EP3178659B1 EP 3178659 B1 EP3178659 B1 EP 3178659B1 EP 15829700 A EP15829700 A EP 15829700A EP 3178659 B1 EP3178659 B1 EP 3178659B1
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EP
European Patent Office
Prior art keywords
paper
transparent portions
portions
monohydric
printing
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.)
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EP15829700.2A
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German (de)
French (fr)
Other versions
EP3178659A4 (en
EP3178659A2 (en
Inventor
Arkadiy Vladimirovich Trachuk
Andrey Borisovich Kuryatnikov
Igor Vasilievich Pavlov
Georgiy Valentinovich KORNILOV
Elena Mikhailovna Fedorova
Alexandr Igorevich MOCHALOV
Mikhail Anatolievich Ostrerov
Nikolay Vasilievich Khomutinnikov
Igor Olegovich Govyazin
Oleg Stanislavovich Busyrev
Nikolay Nikolaevich PESTOV
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Aktsionernoe Obshchestvo "goznak"
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Aktsionernoe Obshchestvo "goznak"
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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
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/351—Translucent or partly translucent parts, e.g. windows
    • 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
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41D—APPARATUS FOR THE MECHANICAL REPRODUCTION OF PRINTING SURFACES FOR STEREOTYPE PRINTING; SHAPING ELASTIC OR DEFORMABLE MATERIAL TO FORM PRINTING SURFACES
    • B41D3/00—Casting stereotype plates; Machines, moulds, or devices therefor
    • 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
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
    • B42D25/24—Passports
    • 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
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
    • B42D25/29—Securities; Bank notes
    • 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
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • 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
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/40—Manufacture
    • B42D25/405—Marking
    • B42D25/415—Marking using chemicals
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/06—Alcohols; Phenols; Ethers; Aldehydes; Ketones; Acetals; Ketals
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/16—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising curable or polymerisable compounds
    • 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
    • D21H21/26—Agents rendering paper transparent or translucent
    • 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
    • D21H21/48—Elements suited for physical verification, e.g. by irradiation
    • 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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/50—Spraying or projecting

Definitions

  • the invention relates to the pulp and paper industry, and particularly to the manufacture of paper for producing banknotes, checks, certificates, bills, passports, identity cards, fuel vouchers, entertainment tickets, and other documents requiring protection against counterfeit.
  • a method is known ( JP2-127599, 16.05.1990 ) to obtain the imitation of watermarks on paper, in which a liquid composition obtained by mixing paraffin, oil and a saturated fatty acid with a resin solution in an organic solvent is applied onto the paper using a printing method.
  • a method is known ( GB1139487, 08.01.1969 ) to obtain the imitation of watermarks, according to which method a composition comprising hexamethoxymethylmelamine, a curing agent and a colorless polar solvent is applied to the paper.
  • thermosetting resin in an organic solvent in the presence of a curing agent. It was particularly suggested to use epoxy resins as the thermosetting resin. In this case, after evaporating the solvent and curing the thermosetting resin, transparent portions simulating the watermark are formed on the paper.
  • a disadvantage of this technical solution is that the epoxy resins are characterized by a high dynamic viscosity at a temperature of 25Ā°C and, therefore, prepared solutions based on the epoxy resins in organic solvents at a concentration of more than 50% penetrate poorly into the paper structure and, after curing, form a solid film on the surface of the paper, which film creates difficulties in the subsequent printing of these paper portions.
  • use of solutions having a concentration of less than 50% does not allow to introduce into the paper a sufficient amount of the resin to provide a desired transparency.
  • a problem to be solved by the invention is the preparation of transparent portions on paper without the formation, on a paper surface, of solid films hindering a subsequent printing process.
  • the glycidyl ethers of monohydric and polyhydric alcohols are dissolved in an organic solvent in a mass ratio of from 30% to 90%.
  • the solutions of the glycidyl ethers of monohydric and polyhydric alcohols in an organic solvent are applied by a printing method onto paper portions of a thickness no more than 80 ā‡ m, which have been produced in the paper during sheet formation on a paper making machine.
  • the transparent portions have a shape of geometrical figures, symbols, letters or numbers that are visible in transmitted light.
  • printing images are applied onto the paper having the transparent portions.
  • printing images are preliminary applied onto the paper, and then the impregnation of the paper is performed to obtain the transparent portions.
  • a paper having transparent portions, said paper being manufactured by the claimed method is defined in claim 7.
  • These compounds are colorless or pale yellow low-viscous liquids that contain epoxy groups in a mass fraction from 7.5% to 30%, and are well compatible with all known epoxy resin curing agents (hardeners).
  • hardeners For example, aliphatic or aromatic polyamines, acid anhydrides, Lewis acids, etc. can be used for their curing. Isopropyl alcohol, ethyl acetate, propyl acetate, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, and also their mixtures, etc. are used as the solvents for these compounds.
  • a dynamic viscosity of the glycidyl ethers of monohydric and polyhydric alcohols at a temperature of 25Ā°C has to be not more than 150 mPa ā‡ s, or, more preferably, not more than 50 mPa ā‡ s. If their dynamic viscosity at a temperature of 25Ā°C exceeds 150 mPa ā‡ s, when the product is dissolved in an organic solvent in a mass ratio of more than 50%, problems associated with deterioration of penetration of the resulting solution into the paper structure are observed.
  • Other compounds containing epoxy groups may be added to the solutions of the glycidyl ethers of monohydric and polyhydric alcohols.
  • homooligomeric epichlorohydrin diglycidyl ether, alkyl phenol monoglycidyl ether, tert-butylphenol monoglycidyl ether can be used as these compounds.
  • compounds which are soluble in organic solvents, which have luminescence properties when irradiated with UV radiation at an excitation wavelength of 365 nm or 254 nm, and which also have absorption properties in IR region of spectrum may be added to the solutions of the glycidyl ethers of monohydric and polyhydric alcohols.
  • the solutions of glycidyl ethers of monohydric and polyhydric alcohols in organic solvents are applied onto predetermined portions of paper by printing methods.
  • a deep printing, screen printing or flexographic printing method can be used.
  • these solutions can be applied onto paper using anilox rolls having a screen ruling of 60-120 lines/cm 2 and an ink receptivity of 10-24 cm 3 /m 2 .
  • the solution viscosity measured on a funnel with an opening diameter of 4 mm should be in the range of 10-35 seconds, or even more preferably, in the range of 10-15 seconds.
  • the solutions can be applied onto predetermined portions simultaneously on both sides of the paper.
  • Formation of transparent portions after applying the solutions onto the paper by printing methods is performed conventionally in two stages. At a first, shortest stage, evaporation of the solvent and also absorption of the solution into the paper occur. To speed up the process at this stage, it is advisable to heat the paper to a temperature of 85-140Ā°C. In a second stage which is the most durable in time and is fully completed already on the reel or stack, the solution soaked into the paper undergoes a final curing. This stage normally lasts for 3-4 days after applying the solution onto the paper.
  • the paper is manufactured on a cylinder paper making machine or a fourdrinier former. It may contain wood, cotton pulp, and also synthetic fibers (capron, polyester) in its composition. Furthermore, the paper composition may contain fillers (titanium dioxide), additives to enhance the strength of paper in a dry and wet state (sodium salt of carboxymethyl cellulose, polyamide(amine) epichlorohydrin resin), materials for paper sizing in mass (alkyl ketene dimers), dyes (direct dyes, acid dyes).
  • fillers titanium dioxide
  • additives to enhance the strength of paper in a dry and wet state sodium salt of carboxymethyl cellulose, polyamide(amine) epichlorohydrin resin
  • materials for paper sizing in mass alkyl ketene dimers
  • dyes direct dyes, acid dyes.
  • the paper is sized from the surface with an aqueous solution of polyvinyl alcohol, and also, which is less preferable, with aqueous dispersions of polyurethane, acrylate, or styrene-acrylate copolymer. If necessary, the paper may contain watermarks, fibers, filaments, and other security features.
  • the solutions are preferably applied onto the paper portions of a thickness not more than 80 ā‡ m. This enables to obtain transparent portions with a high transparency on the paper after infiltration of the solution and curing.
  • the paper used for the production of banknotes has a thickness of 100-130 ā‡ m at a grammage of 90 g/m 2 .
  • portions of a predetermined shape and size which have a smaller thickness as compared to the thickness of the paper, can be formed in the paper web during sheet formation.
  • a dandy roll or design cylinder having watertight elements (watermarks) which have the size and shape of these portions.
  • the thickness of the paper can be varied by rasterization and by changing the thickness of these watertight elements.
  • the portions of a smaller thickness can be formed on the paper by using a method described in US6402888, 11.06.2002 .
  • the transparent portions obtained by applying the solutions onto paper by printing methods should have a shape and size envisaged by the design of a product.
  • they may be located on a sheet of paper symmetrically to overlapping fragments of a watermark ( RU2475578, 20.02.2013 ).
  • they are shaped and sized according to the overlapping fragments of the watermark.
  • the transparent portions may have a square, circle, ellipse shape, etc.
  • the transparent portions may be printed by conventional printing methods used for the production of valuable documents and, in particular, banknotes.
  • the printing at the transparent portions can be carried out by a offset printing, metallographic printing, relief printing or screen printing method.
  • the printing of predetermined portions of paper is performed firstly by the above-mentioned printing methods, and then the solution is applied onto these predetermined portions in order to obtain the transparent portions.
  • a transparency level of the transparent portions was evaluated by measuring an optical density of the paper by means of an X-Rite transmission densitometer. Meanwhile, a decrease in optical density meant an increase in the transparency of the paper.
  • a banknote paper having a grammage 90 g/m 2 was produced on a cylinder paper making machine according to a known technology, using a design cylinder having watertight elements fixed on a mesh in certain positions.
  • the paper was sized in an impregnating bath with a 4% aqueous solution of PVA. At this time, symmetrically to an arrangement of the watertight elements on the mesh, portions whose thickness was less than the thickness of the paper (110 ā‡ m) and varied in the range of 60-96 ā‡ m were formed on the paper.
  • the solution was applied onto both the paper portions of the thickness 110 ā‡ m and the thinner portions formed on the paper symmetrically to the arrangement of the watertight elements. After drying and full curing of the solution (after 72 hours), transparent portions visible in transmission mode were formed in those locations where the solution had been applied onto the paper.
  • Example 2 The same as in Example 2, except that diethylene glycol diglycidyl ether (dynamic viscosity at 25Ā°C is 38 mPa ā‡ s) was used in the solution composition instead of the polyoxypropylentriole triglycidyl ether.
  • diethylene glycol diglycidyl ether dynamic viscosity at 25Ā°C is 38 mPa ā‡ s
  • Example 2 The same as in Example 2, except that butyl cellosolve monoglycidyl ether (dynamic viscosity at 25Ā°C is 6 mPa ā‡ s) was used in the solution composition instead of the polyoxypropylentriole triglycidyl ether.
  • butyl cellosolve monoglycidyl ether dynamic viscosity at 25Ā°C is 6 mPa ā‡ s
  • Example 2 The same as in Example 2, except that n-butanol monoglycidyl ether (dynamic viscosity at 25Ā°C is 1.5 mPa ā‡ s) was used in the solution composition instead of the polyoxypropylentriole triglycidyl ether.
  • n-butanol monoglycidyl ether dynamic viscosity at 25Ā°C is 1.5 mPa ā‡ s
  • Example 2 The same as in Example 2, except that a solution of the following composition was used for printing: Polyoxypropylentriole triglycidyl ether (dynamic viscosity at 25Ā°C is 115 mPa ā‡ s) 25 parts Isopropyl alcohol 36 parts Curing agent PEPA 3 parts
  • Example 2 The same as in Example 2, except that a solution of the following composition was used for printing: Polyoxypropylentriole triglycidyl ether (dynamic viscosity at 25Ā°C is 115 mPa ā‡ s) 25 parts Isopropyl alcohol 31 parts Curing agent XT-116, component B ("CHIMEX Limited", CJSC) 8 parts
  • Example 2 The same as in Example 2, except that a low-viscosity resin ELAD EDB (dynamic viscosity at 25Ā°C is 950 mPa ā‡ s) was used in the solution composition instead of the polyoxypropylentriole triglycidyl ether.
  • ELAD EDB dynamic viscosity at 25Ā°C is 950 mPa ā‡ s
  • the claimed method allows those portions to be obtained on the paper which have, as compared to the known prior art, a higher transparency without forming, on the surface of the paper, the films hindering the subsequent printing process.
  • the result is achieved by applying onto the paper the solutions of glycidyl ethers of monohydric and polyhydric alcohols which are well absorbed in the paper structure, even when a concentration of the glycidyl ethers of monohydric and polyhydric alcohols in the solution is more than 50%.
  • the greatest effect of using the method of the invention is achieved for papers having a high degree of opacity, which are used for example for the production of banknotes or other valuable documents.
  • the invention is industrially applicable in the pulp and paper industry, in particular, for the manufacture of paper for producing banknotes, checks, certificates, bills, passports, identity cards, fuel vouchers, entertainment tickets, and other documents requiring protection against counterfeit.

Description

    Technical field
  • The invention relates to the pulp and paper industry, and particularly to the manufacture of paper for producing banknotes, checks, certificates, bills, passports, identity cards, fuel vouchers, entertainment tickets, and other documents requiring protection against counterfeit.
    • Prior art
  • A method is known ( JP2-127599, 16.05.1990 ) to obtain the imitation of watermarks on paper, in which a liquid composition obtained by mixing paraffin, oil and a saturated fatty acid with a resin solution in an organic solvent is applied onto the paper using a printing method.
  • Furthermore, a method is known ( GB1139487, 08.01.1969 ) to obtain the imitation of watermarks, according to which method a composition comprising hexamethoxymethylmelamine, a curing agent and a colorless polar solvent is applied to the paper.
  • A closest prior art to the claimed technical solution is a method ( US3140959, 14.07.1964 ) to obtain paper with a simulated watermark, in which the paper portions corresponding to a watermark design are impregnated with a solution of a thermosetting resin in an organic solvent in the presence of a curing agent. It was particularly suggested to use epoxy resins as the thermosetting resin. In this case, after evaporating the solvent and curing the thermosetting resin, transparent portions simulating the watermark are formed on the paper.
  • A disadvantage of this technical solution is that the epoxy resins are characterized by a high dynamic viscosity at a temperature of 25Ā°C and, therefore, prepared solutions based on the epoxy resins in organic solvents at a concentration of more than 50% penetrate poorly into the paper structure and, after curing, form a solid film on the surface of the paper, which film creates difficulties in the subsequent printing of these paper portions. On the other hand, use of solutions having a concentration of less than 50% does not allow to introduce into the paper a sufficient amount of the resin to provide a desired transparency.
    • Disclosure of the invention
  • A problem to be solved by the invention is the preparation of transparent portions on paper without the formation, on a paper surface, of solid films hindering a subsequent printing process.
  • This technical result is particularly noticeable on papers having a high degree of opacity, which are used for example for the production of banknotes, because the solution compositions known from the prior art do not enable to obtain portions having a sufficiently high transparency on such papers by impregnation.
  • The technical result is achieved by the method as defined in claim 1. Glycidyl ethers of monohydric and polyhydric alcohols expressed by the following general formula are preferably used as the compounds having epoxy groups:
    Figure imgb0001
     where n = 1-3, and R is a residue of the monohydric or polyhydric alcohol.
  • Advantageously the glycidyl ethers of monohydric and polyhydric alcohols are dissolved in an organic solvent in a mass ratio of from 30% to 90%.
  • Advantageously the solutions of the glycidyl ethers of monohydric and polyhydric alcohols in an organic solvent are applied by a printing method onto paper portions of a thickness no more than 80 Āµm, which have been produced in the paper during sheet formation on a paper making machine.
  • In particular, the transparent portions have a shape of geometrical figures, symbols, letters or numbers that are visible in transmitted light.
  • Specifically, printing images are applied onto the paper having the transparent portions. In another embodiment, printing images are preliminary applied onto the paper, and then the impregnation of the paper is performed to obtain the transparent portions.
  • A paper having transparent portions, said paper being manufactured by the claimed method is defined in claim 7.
  • Monoglycidyl ether of n-butanol, butyl cellosolve monoglycidyl ether, 2-ethylhexanol monoglycidyl ether, diethylene glycol diglycidyl ether, polyoxypropylene glycol diglycidyl ether, polyoxypropylentriole triglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, and others are used in the method of the invention as the glycidyl ethers of monohydric and polyhydric alcohols. Moreover, to achieve the required effect, said compounds may be used either separately, or as a mixture of two or more compounds.
  • These compounds are colorless or pale yellow low-viscous liquids that contain epoxy groups in a mass fraction from 7.5% to 30%, and are well compatible with all known epoxy resin curing agents (hardeners). For example, aliphatic or aromatic polyamines, acid anhydrides, Lewis acids, etc. can be used for their curing. Isopropyl alcohol, ethyl acetate, propyl acetate, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, and also their mixtures, etc. are used as the solvents for these compounds.
  • In accordance with the invention, a dynamic viscosity of the glycidyl ethers of monohydric and polyhydric alcohols at a temperature of 25Ā°C has to be not more than 150 mPaĀ·s, or, more preferably, not more than 50 mPaĀ·s. If their dynamic viscosity at a temperature of 25Ā°C exceeds 150 mPaĀ·s, when the product is dissolved in an organic solvent in a mass ratio of more than 50%, problems associated with deterioration of penetration of the resulting solution into the paper structure are observed.
  • Other compounds containing epoxy groups may be added to the solutions of the glycidyl ethers of monohydric and polyhydric alcohols. For example, homooligomeric epichlorohydrin diglycidyl ether, alkyl phenol monoglycidyl ether, tert-butylphenol monoglycidyl ether can be used as these compounds. In addition, in order to protect against counterfeiting, compounds which are soluble in organic solvents, which have luminescence properties when irradiated with UV radiation at an excitation wavelength of 365 nm or 254 nm, and which also have absorption properties in IR region of spectrum, may be added to the solutions of the glycidyl ethers of monohydric and polyhydric alcohols.
  • The solutions of glycidyl ethers of monohydric and polyhydric alcohols in organic solvents (hereinafter the solutions) are applied onto predetermined portions of paper by printing methods. To do this, a deep printing, screen printing or flexographic printing method can be used. For example, when a flexographic printing method is used, these solutions can be applied onto paper using anilox rolls having a screen ruling of 60-120 lines/cm2 and an ink receptivity of 10-24 cm3/m2. In this case, the solution viscosity measured on a funnel with an opening diameter of 4 mm, should be in the range of 10-35 seconds, or even more preferably, in the range of 10-15 seconds.
  • If necessary to improve the transparency, the solutions can be applied onto predetermined portions simultaneously on both sides of the paper.
  • Formation of transparent portions after applying the solutions onto the paper by printing methods is performed conventionally in two stages. At a first, shortest stage, evaporation of the solvent and also absorption of the solution into the paper occur. To speed up the process at this stage, it is advisable to heat the paper to a temperature of 85-140Ā°C. In a second stage which is the most durable in time and is fully completed already on the reel or stack, the solution soaked into the paper undergoes a final curing. This stage normally lasts for 3-4 days after applying the solution onto the paper.
  • The paper is manufactured on a cylinder paper making machine or a fourdrinier former. It may contain wood, cotton pulp, and also synthetic fibers (capron, polyester) in its composition. Furthermore, the paper composition may contain fillers (titanium dioxide), additives to enhance the strength of paper in a dry and wet state (sodium salt of carboxymethyl cellulose, polyamide(amine) epichlorohydrin resin), materials for paper sizing in mass (alkyl ketene dimers), dyes (direct dyes, acid dyes). During the manufacturing process, the paper is sized from the surface with an aqueous solution of polyvinyl alcohol, and also, which is less preferable, with aqueous dispersions of polyurethane, acrylate, or styrene-acrylate copolymer. If necessary, the paper may contain watermarks, fibers, filaments, and other security features.
  • The solutions are preferably applied onto the paper portions of a thickness not more than 80 Āµm. This enables to obtain transparent portions with a high transparency on the paper after infiltration of the solution and curing. Typically, the paper used for the production of banknotes has a thickness of 100-130 Āµm at a grammage of 90 g/m2. In such paper, portions of a predetermined shape and size, which have a smaller thickness as compared to the thickness of the paper, can be formed in the paper web during sheet formation. For instance, to fabricate these portions in the sheet formation process using a paper making machine, one can use a dandy roll or design cylinder having watertight elements (watermarks) which have the size and shape of these portions. In this case, the thickness of the paper can be varied by rasterization and by changing the thickness of these watertight elements. Furthermore, the portions of a smaller thickness can be formed on the paper by using a method described in US6402888, 11.06.2002 .
  • The transparent portions obtained by applying the solutions onto paper by printing methods (hereinafter the transparent portions) should have a shape and size envisaged by the design of a product. For example, they may be located on a sheet of paper symmetrically to overlapping fragments of a watermark ( RU2475578, 20.02.2013 ). In this case, they are shaped and sized according to the overlapping fragments of the watermark. In the simplest case, the transparent portions may have a square, circle, ellipse shape, etc.
  • After complete curing of the solution, the transparent portions may be printed by conventional printing methods used for the production of valuable documents and, in particular, banknotes. For example, the printing at the transparent portions can be carried out by a offset printing, metallographic printing, relief printing or screen printing method. Furthermore, it is possible that the printing of predetermined portions of paper is performed firstly by the above-mentioned printing methods, and then the solution is applied onto these predetermined portions in order to obtain the transparent portions.
  • A transparency level of the transparent portions was evaluated by measuring an optical density of the paper by means of an X-Rite transmission densitometer. Meanwhile, a decrease in optical density meant an increase in the transparency of the paper.
  • Next, the claimed method will be explained in details by examples. The content of the components of the solutions in all examples is expressed in parts by mass.
    • The best examples of embodiment of the invention Example 1.
  • A banknote paper having a grammage 90 g/m2 was produced on a cylinder paper making machine according to a known technology, using a design cylinder having watertight elements fixed on a mesh in certain positions. The paper was sized in an impregnating bath with a 4% aqueous solution of PVA. At this time, symmetrically to an arrangement of the watertight elements on the mesh, portions whose thickness was less than the thickness of the paper (110 Āµm) and varied in the range of 60-96 Āµm were formed on the paper.
    • Example 2.
  • A solution of the following composition was applied onto the paper prepared in accordance with Example 1 by a flexographic printing method:
    Polyoxypropylentriole triglycidyl ether (dynamic viscosity at 25Ā°C is 115 mPaĀ·s) 35 parts
    Ethyl acetate 25 parts
    Curing agent PEPA 4 parts
  • The solution was applied onto both the paper portions of the thickness 110 Āµm and the thinner portions formed on the paper symmetrically to the arrangement of the watertight elements. After drying and full curing of the solution (after 72 hours), transparent portions visible in transmission mode were formed in those locations where the solution had been applied onto the paper.
    • Example 3.
  • The same as in Example 2, except that diethylene glycol diglycidyl ether (dynamic viscosity at 25Ā°C is 38 mPaĀ·s) was used in the solution composition instead of the polyoxypropylentriole triglycidyl ether.
    • Example 4.
  • The same as in Example 2, except that butyl cellosolve monoglycidyl ether (dynamic viscosity at 25Ā°C is 6 mPaĀ·s) was used in the solution composition instead of the polyoxypropylentriole triglycidyl ether.
    • Example 5.
  • The same as in Example 2, except that n-butanol monoglycidyl ether (dynamic viscosity at 25Ā°C is 1.5 mPaĀ·s) was used in the solution composition instead of the polyoxypropylentriole triglycidyl ether.
    • Example 6.
  • The same as in Example 2, except that a solution of the following composition was used for printing:
    Polyoxypropylentriole triglycidyl ether (dynamic viscosity at 25Ā°C is 115 mPaĀ·s) 25 parts
    Isopropyl alcohol 36 parts
    Curing agent PEPA 3 parts
    • Example 7.
  • The same as in Example 2, except that a solution of the following composition was used for printing:
    Polyoxypropylentriole triglycidyl ether (dynamic viscosity at 25Ā°C is 115 mPaĀ·s) 25 parts
    Isopropyl alcohol 31 parts
    Curing agent XT-116, component B ("CHIMEX Limited", CJSC) 8 parts
    • Example 8 (comparative).
  • The same as in Example 2, except that a low-viscosity resin ELAD EDB (dynamic viscosity at 25Ā°C is 950 mPaĀ·s) was used in the solution composition instead of the polyoxypropylentriole triglycidyl ether.
  • Analysis of the results obtained has shown that the application of the solutions prepared according to the claimed method (Examples 2-7) onto the paper allowed a higher transparency to be obtained (an optical density value in transmission mode turned out less by 5-35%) as compared to the closest prior art (Example 8). Furthermore, these solutions were absorbed efficiently into the paper structure without forming, on a surface of the paper, films hindering the subsequent printing process. And the best result in terms of improving the transparency was obtained when applying these solutions onto the paper portions with a thickness of not more than 80 Āµm.
  • Thus, the claimed method allows those portions to be obtained on the paper which have, as compared to the known prior art, a higher transparency without forming, on the surface of the paper, the films hindering the subsequent printing process. The result is achieved by applying onto the paper the solutions of glycidyl ethers of monohydric and polyhydric alcohols which are well absorbed in the paper structure, even when a concentration of the glycidyl ethers of monohydric and polyhydric alcohols in the solution is more than 50%. Moreover, the greatest effect of using the method of the invention is achieved for papers having a high degree of opacity, which are used for example for the production of banknotes or other valuable documents.
    • Industrial applicability
  • The invention is industrially applicable in the pulp and paper industry, in particular, for the manufacture of paper for producing banknotes, checks, certificates, bills, passports, identity cards, fuel vouchers, entertainment tickets, and other documents requiring protection against counterfeit.

Claims (7)

  1. A method for manufacturing paper having transparent portions of certain shape, in which the paper portions are impregnated locally with a solution of compounds having epoxy groups in the presence of a curing agent, characterized in that glycidyl ethers of monohydric and polyhydric alcohols having a dynamic viscosity of not more than 150 mPaĀ·s at a temperature of 25Ā°C are used as the compounds having epoxy groups.
  2. A method according to claim 1, characterized in that the glycidyl ethers of monohydric and polyhydric alcohols are dissolved in an organic solvent in a mass ratio of from 30% to 90%.
  3. A method according to claim 1 or claim 2, characterized in that the solutions of the glycidyl ethers of monohydric and polyhydric alcohols are applied by a printing method onto the paper portions of a thickness not more than 80 Āµm, which have been produced in the paper during sheet formation on a paper making machine.
  4. A method according to any one of claims 1 to 3, characterized in that the transparent portions have a shape of geometrical figures, symbols, letters or numbers that are visible in transmitted light.
  5. A method according to any one of claims 1 to 4, characterized in that printing images are applied onto the paper having the transparent portions.
  6. A method according to any one of claims 1 to 4, characterized in that printing images are preliminary applied onto the paper, and then the impregnation of the paper is performed to obtain the transparent portions.
  7. Paper having transparent portions, being manufactured by the method as defined in any of claims 1 to 6.
EP15829700.2A 2014-08-06 2015-07-29 Method for preparing paper having transparent portions, and paper having transparent portions prepared using said method Active EP3178659B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU2014132441/12A RU2568398C1 (en) 2014-08-06 2014-08-06 Method of making paper with transparent sections, and paper with transparent sections made with this method
PCT/RU2015/000477 WO2016022046A2 (en) 2014-08-06 2015-07-29 Method for preparing paper having transparent portions, and paper having transparent portions prepared using said method

Publications (3)

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EP3178659A2 EP3178659A2 (en) 2017-06-14
EP3178659A4 EP3178659A4 (en) 2018-03-21
EP3178659B1 true EP3178659B1 (en) 2019-07-24

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KR (1) KR102185111B1 (en)
RU (1) RU2568398C1 (en)
WO (1) WO2016022046A2 (en)

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DE102020108081A1 (en) 2020-03-24 2021-09-30 Koenig & Bauer Ag Method for producing a security feature effective as a see-through register on a security document and a security document with a security feature effective as a see-through register on a security document
DE102020108080A1 (en) 2020-03-24 2021-09-30 Koenig & Bauer Ag Method for producing a security feature effective as a see-through register on a security document, method for producing security documents and security document

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RU2639809C1 (en) * 2017-04-20 2017-12-22 ŠŠŗцŠøŠ¾Š½ŠµŃ€Š½Š¾Šµ Š¾Š±Ń‰ŠµŃŃ‚Š²Š¾ "Š“ŠžŠ—ŠŠŠš" Method of manufacture of paper with transparent sites and paper with transparent sites, manufactured by this method
SE2050456A1 (en) * 2020-04-21 2021-10-22 Rise Innventia Ab Transparent paper or cardboard substrate and method for its production

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DE102020108081A1 (en) 2020-03-24 2021-09-30 Koenig & Bauer Ag Method for producing a security feature effective as a see-through register on a security document and a security document with a security feature effective as a see-through register on a security document
DE102020108080A1 (en) 2020-03-24 2021-09-30 Koenig & Bauer Ag Method for producing a security feature effective as a see-through register on a security document, method for producing security documents and security document

Also Published As

Publication number Publication date
RU2568398C1 (en) 2015-11-20
WO2016022046A3 (en) 2016-03-17
EP3178659A4 (en) 2018-03-21
WO2016022046A2 (en) 2016-02-11
KR20170041818A (en) 2017-04-17
EP3178659A2 (en) 2017-06-14
KR102185111B1 (en) 2020-12-02

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