CA1279158C - Security paper - Google Patents
Security paperInfo
- Publication number
- CA1279158C CA1279158C CA 524500 CA524500A CA1279158C CA 1279158 C CA1279158 C CA 1279158C CA 524500 CA524500 CA 524500 CA 524500 A CA524500 A CA 524500A CA 1279158 C CA1279158 C CA 1279158C
- Authority
- CA
- Canada
- Prior art keywords
- paper
- granules
- particles
- paper according
- pigment
- 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.)
- Expired - Lifetime
Links
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S283/00—Printed matter
- Y10S283/904—Credit card
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/916—Fraud or tamper detecting
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
- Y10T428/24901—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material including coloring matter
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24934—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including paper layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31971—Of carbohydrate
- Y10T428/31993—Of paper
- Y10T428/31996—Next to layer of metal salt [e.g., plasterboard, etc.]
Abstract
ABSTRACT
Paper embodying for purposes of identification one or more pigments, inconspicuous in daylight but visible on inspection in darkened surroundings or after illumination at predetermined wavelength from an artificial source, wherein the pigment is in the form of granules which are of 30 to 500 microns particle size and, to secure contrast between the pigment and background in said inspection, are essentially free of finer particles.
Paper embodying for purposes of identification one or more pigments, inconspicuous in daylight but visible on inspection in darkened surroundings or after illumination at predetermined wavelength from an artificial source, wherein the pigment is in the form of granules which are of 30 to 500 microns particle size and, to secure contrast between the pigment and background in said inspection, are essentially free of finer particles.
Description
93L5~3 - l - 21739-107 SECURITY PAPER
The invention relates to identified paper for security and other purposes.
In many applications paper is required to be identifi-able as to source or authenticity as well as, in security applica-tions, difficult to counterfeit. Desirably also, attempts to falsify documents should irreversibly change the paper.
One approach has been -that of Aussedat Rey S.A. in their French Patent Application No. 80 06336 (2 ~78 695) laid open on September 25, 1981 in which luminescent particles are dispersed in the paper, showing up in ultraviolet light. Combinations of pig-ments can be used, as mixed agglomerates or added separately, and pigments sensitive to falsification procedures can be chosen.
There are however problems in insufficiently con-trolled incorpora-tion in the paper, losses on the machine, and obtrusiveness in ordinary use of the paper, as well as a wide variation in particle size.
We have studied the above approach and found that a key aspect is the particle size. Particles should neither be so large that they are distracting in the use of the paper, nor so small as not to be identifiable by eye when the paper is checked. Parti-cles that are too ,~
~279~8 '"
small merge into a general background and thus lose their identifying characteristics. Further, we have recognised that not only the predominant particle size but an absence of background from small particles, not S individually appreciable, is important if the quick checking of papers for source or authenticity that is necessary in practical use is to be achieved.
m e invention accordingly provides paper embodying for purposes of identification one or more pigments, inconspicuous in daylight but visible on inspection in darkened surroundings or after illumination at predetermined wavelength from an artificial source, wherein the pigment is in the form of granules which are of 30 to 500 microns, preferably 100 to 230 or 250 microns particle size and, to secure contrast between the pigment and backgr~und on said inspection, are essentially free of finer particles.
It is impracticable to quantify the limit for fine particles, but by careful production of the granules in the first place and by subs~quent sieving they can be reduced to a small proportion, certainly under 5% where the small particles of commercially available pigment are concerned and likely under 1~ by weight. The test is ; whether on inspection of the final paper there is contrast between a visually unreactive background and the granules. A paper according to the invention, ~LZ7~1S~3 - using fluorescent particles, can for example be viewed under ordinary room lighting by passing a U.V. lamp across it, when distinctive individual spots of light flash up against a background that, relative to them, is dark. Under similar c-,nditions a prior art product made without control of the granule size shows a diffuse and generalised reaction, uncontrolled and indistinct, against a background of light from individually indistinguishable particles.
The granules may for example be formed of a resin containing a light-reacting dye or of pre-formed light-reacting particles resin bonded, allowing close and pre-determined control of the particle size.
Such pre-formed pigment particles are conveniently themselves of a resin containing a light reacting dye, but there is no restriction to these and for example pigment materials light reactive per se, such as phosphorescent zinc sulphide particles, may be bonded~
~L279~5~3 An important subsidiary feature of the invention lies in a practical and convenient method of making the granules from commercially available pigments, which are supplied in very finely divided form. ~hus suitably the granules are formed by adding a quantity of a liquid resin binder to the particles and tumbling until aggregates constituting the granules have been formed, said quantity of binder being sufficient to aggregate the particles but not to form a continuous liquid phase.
In an important further embodiment, allowing far more particular characterisation of a paper, for example as to period as well as source of manufacture, the pre-formed particles are themselves of smaller particles~ preferably aggregated by a process as a~ove.
Desirably for security applications the granules are dispersed in the substance of the paper followiny incorporation in a paper-making stock, particularly immediately prior to the headbox. However, where identification rather than security as such is the important aspect, it is convenient if the granules are present as a coating or as separated indicia, applied to the paper.
Such indicia can be very economical of the pigments, a carbonless copy paper set for example needing only to carry, essentially only on one sheet of the set, sufficiently frequent indicia that one or more will appear on each quch sheet.
~27~ i8 Thus the granules may be in various forms, e.g.
aggregates of commercially available luminescent pigments used singly or to make mixed granules, or resins containing luminescent dye ground to form the granules, of granules of zinc or other phosphorescent compounds. It is also possible to use a combination of a resin, containing luminescent dye, acting as a binder for other pigments either in an aggregation process or in a direct process of formation of a block and grinding to size. The resin, or resin-bonded,granules are particularly suited to being incorporated in paper stock as they are not susceptible to size reduction in the paper-making process, partlcularly physical break-up in the refiners of the stock preparation system.
The luminescent material may be either fluorescent or phosphorescent. For example papex produced may be intended to be observed under U.V. light, particularly with the convenient battery operated low power U.V. sources now available for hand-held use, the particles fluorescing ` 20 in one or more colours. Each individual particle may show a single colour or a composite of two or more different colours. Paper may alternatively or in addition contain phosphorescent particles luminescing under the influence of daylight, and if such paper is observed in a darkened room, or a dark box, the sranules will continue to glow.
iL2~ i8 ~, In the aspect of the invention where resin-dissolved fluorescent dyes are used, suitable dyes and resins are known in themselves, available for example from Swada (London) Ltd., Sugar House Lane, London E.15 in their "Fiesta" (Trade M~lr]~) pigment range. The fluorescence of organic dyes is associated with the individual molecules of the dyes, and in order for them to fluoresce efficiently. they are molecularly dissolved in fairly low concentrations, for example from about 1 to 4%. ~s the dyes are organic in nature it is necessary to have an organic medium to take them into ~olution, and in order to have a pigment it is essential for medium to be solid. One type of material that meets these requirements is a melamine formaldehyde resin modified with sufficient aromatic sulphonamide to form a brittle thermoplastic or thermoset product which can be ground to the required particle size. Various red and orange shades are available with yellow, blue and green also.
The aggregation process descri~ed above was developed primarily because commercial luminescent pigments are generally available only in standard particle sizes of perhaps 3 to 5 microns. The agglomeration process generates particles of the larger size suited to the present use. However, luminescent pigments such as ~2~9~S~3 , the "Fiesta" range are in fact solutions of luminescent dyes in a base resin, and are made from block form by grinding. Where a single pic~ent is sufficient it can be made direct in the required size.
The question whether or not a mixed aggregate is necessary depends partly on uniqueness of identification, but also on the apparent colour of the particle required.
In cases where the required particle colour is that of one of the available luminescent dyes, one can simply use a particle of the right size ground from a block using such a dye. However, mixed apparent shades, for example greens not directly available, can be given by mixed aggregation of fine blue and yellow particles.
The invention thus conveniently uses:
- two or more luminescers, for ready exclusive identification - aggregates readily incorporated in papermaking and not degrading in size - particles convenient for ~bservation by reason of their size In a further aspect the invention provides a process of making pigment agglomerates, and the agglomerates produced, wherein pigments as ~bove are coated in reactive binder and formed directly or indirectly into the agglomerates. Preferably the coating is achieved by tumbling of pigment and binder and the tumbling continued ~7~58 until the desired agglomerates have formed. It is particularly advantageous to form sub-agglomerates of individual pigments in this way, and thencombine them into composite agglomerates. Highly characteristic paper can then be made, with the individual pigments in the agglomerates readily identified.
The tumbling is an essentially solid phase process operated with only sufficient liquid binder to coat the particles, but the use of a carrier solvent for theresin or other binder is not excluded. The agglomeration process can be closely controlled and the product graded, any undersize agglomerates being returned direct to the agglomeration process and any oversize product ground and likewise returned.
It will be appreciated that binder coating of the pigment may be achieved by other techniques. For example as referred to earlier herein, the pigment may be disposed in reactive binder and the binder cured to form a blck subsequentl~ ground to form the agglomerates.
Composite agglomerates if required are then made from separately made sub-ag~lomerates by a further agglomeration step.
In a particular process, pigment particles of 3 - 5~k~(micron) or other convenient particle size, are coated with a binder resin containing a cross linking -- 127~1S8 g catalyst, such as ammonium chloride. The binder can for example be a melamine formaldehyde or acrylic resin.
The particles are agglomerated by granulation in the solid phase as described above, to produce larger granules or agglomerates, and the binder is cured naturally or with heating, for example at 105C. The cured granules are sieved to exclude granules outside the desired particle si~e range and the sieved granules added to the paper machine prior to for~ing the web, e.g. in the pulper, chest or approach flow. Alternatively, sub-granules may be prepared from separate pigments, regranulated, and sieved to produce composite granules of two or more colours.
Granules produced in the ~id phase, by this granulation technique, comprise the 3 - 5 micron pigment particles chemically bound together by a fully cross linked binder. Prior agglomerates such as those of Aussedat Rey S.A. are formed in the liquid phase and, although a binder is present, this binder is not cross linked until the paper is dried on the paper machine. Such granules are physically, rather than chemically, agglomeratsd and it is impossible to control their production to a regular distrib~tion or to obtain in one paper different composite granules of two or more colours.
As to the stage of incorporation in the paper, success has been achieved by addition of the granules ~7~
to the thickstock contained in the chest of the paper machine priox to refining, to the refined thickstock in the second chest of the paper machine, and by addition to the size press. However, it has been found to be most beneficial to add the granules to the thinstock immediately prior to theheadbox to obtain the most desirable visual effect.
Particular examples of the use of the invention are as follows:
"Radglo" (Trade Mark~ pigments were used, obtained from Ciba-Gei~y and made by Radiant Colour ~.V.
Europarklaan B 3530 Houthalen, Holland. They comprised an aldehyde-sulfonomide-triazine polycondensation resin with fluorescent dyestuffs, known per se.
1 kg of each pigment powder, comprising particles in the range 3 to 5~ M diameter, was mixed in a stainless steel drum, rotating at 84 rpm and inclined at 30 degrees to the horizontal. An agitator positioned in the drum was rotated at 5000 rpm in the opposite direction to the rotating drum.
180 ml of an aqueous acrylic emulsion, "Acronal"
tTrade Mark) S 360 D, at 25% resin solids containing 0.5% ammonium chloride catalyst weight on resin solids was used. It was a styrene acrylonitrile and acrylic ester ~L2~79158 copolymer dispersion obtained from BASF (U.K.) Ltd., PØ
Box 4, Earl Road, Cheadlehume, Cheshire. An alternative catalyst is p-toluene sulphonic acid. The emulsion was slowly added to the fluorescent pigment powder which formed granules that increased in size as the emulsion was added.
The process was stopped before excessively large granules were formed.
It was noted that in this instance the temperature of the rotating drum had risen from ambient temperature to 30 C as the granulating process continued. It has however been found that the precise quantity of binder required differs from one batch to the next, depending partly on the skill of the operator but also on the : speed of addition, the temperature of the binder, the solids content and the chemical nature of the binder. For example, in a separate run it was found that 125 ml of a 35% solids solution of "Beetle BC 355" (Trade Mark) non-ionic methylated melami`ne formaldehyde resin binder, at 50 C, was sufficient. It was obtained from British Industrial Plastics, PØ Box 6, Pope's Lane, Oldbury, Warley, West Midlands.
The granules were removed from the drum and dried in an oven at 105 C (natural curing or microwave oYen heating are alternatives) for 1 hour to cross link 5 the binder, ar~ the size of the granules produced by the ~279158 .:
process was found to be very suitable at the high drum and agitator rotational speeds used.
The dried granules were sieved to remove granules smaller than 106~M andl~rger than 230 ~M. The small granules were regranulated and the large granules likewise retained for grinding, sieving and regranulation.
White (blue fluorescence), yellow, orange and red granules were produced by the granulation process.
The granules were mixed in the ratio of 4 : 3 : 2 : 2, by volume, and dispersed in water at a concentration of 1%
by weight. The dispersion of granules was pumped into the thinstock of a paper machine immediately prior to the headbox at the rate of 4 Kg granules/tonne paper (0.4 g/m2 on a paper of substance 100 g/m ).
When the paper produced by the addition of the granules was observed under ultra-violet light it was found to contain well distributed, easily observed distinct spots which fluoresced blue, yellow, orange and red~
EXAMPLE II
Two pigments corresponding to 3 - 5 ~M particle size pigments from the "Fiesta" range as referred to earlier herein, namely "Fire Orange A 4" and "Corona Magenta A 10", were prepared by dissolving the dyes (2% by weight~ in a standard aromatic sulphonamide-modified melamine forrhldehy~e resin hS used for 6uch pigrents, curing in - 1;2 79~L5~3 block form and grinding direct to 106 - 230~M Used in making of paper as in Example I these gave a security product with orange and red spots visible with care to the eye in daylight and orange and magenta fluorescence under wide-band U.V. light.
EXAMPLE III
500g of per se conventional fluorescent yellow pigment at 3 - 5 ~M particle size from the "Fiesta" range - was mixed in a rotating drum as in Example I. 150 ml of a polyvinyl acetate emulsion at 50~/O solids, "Vinamul"
R82020 (Trade Mark) was slowly added to the fluorescent pigment powder. It was a polyvinyl alcohol stabilised self cross linking polyvinyl alcohol emulsion obtained from Vinamul Ltd. at Mill Lane, Carshalton, Surrey. The process was stopped before the granules became excessively large. The granules were removed from the drum and allowed to dry at ambient temperature.
The granules were sieved to remove particles smaller than 106~ M and ~rger than 230~M.
Laboratory handsheets containing the granules were produced and were found to contain distinct spots which fluoresced yellow when observed under ultra-violet light.
~2~9~S8 EXAMPLE IV
Phosphorescent pigment 163G, a known zinc sulphide : copper activated pigment obtained from Derby Luminescents at Mill Marsh Lane, Brinsdown, Enfield, Middlesex was used, 25g cf the pigment being weighed into a laboratory beaker. 5g of a polyvinyl acetate emulsion, Vinamul R82020 (Trade Mark), at 50Y~ solids, was slowly added to the pigment and stirred vigorously with a glass rod to form granules.
The granules were removed from the beaker and allowed to dry at ambient temperature.
The dried granules were sieved to remove granules smaller than 106 ~M and larger than 230~ M.
Laboratory handsheets were produced containing the granules within the particle size range of 106~ M to 230~ M.
When thepaper, previously in daylight, was observed in a dark room it was found to contain well distributed easily observed distinct green sp~ts. It was found that the brightness of th~spots could be increased by prior exposure to ultra-violet light. The brightness of the spots was found to diminish with time if the paper was retained in the dark room without further exposure to ultra-violet or visible lignt.
EXAMPLE V
Using a laboratory coater, sheets of A4 size white paper of the kind used as a base paper in the manufacture of 'IDEM' (Registered Trade Mark) carbonless copying paper were coated on one side with 5 grams per square metre of a standard mix of microcapsules, starch particles and carboxymethylcellulose binder as used in such copying paper and in which had been dispersed 0.1% by weight of a fluorescent granule mix as described in Example I.
The other side of each sheet was similarly coated with 8 grams per square metre of a standard dispersion of acid washed montmorillonite clay (sold under the trade name 'Silton') and kaolin and to which 0.1% by weight of the same fluorescent granule mix had been added.
When the dIied paper was observed under ultra-violet light, well distributed easily observed distinct spots were observed on both sides of the paper which fluoresced blue, yellow, orange and red and exhibited a good contrast against the background.
EXAMPLE VI
Using a laboratory coater, sheets of A4 size white paper of the kind used as a base paper in the manufacture of 'IDEM' (Registered Trade Mark) carbonless copying paper were coated on one side with 8 grams per square metre of the following formulation:-~2~9~i8 Grams Water 27.1 Potassium hydroxide (50%) 0.6 Sodium hydroxide (30%) 1.3 Kaolin (sold under the trade name 'Dinkie A') 7.9 Acid washed montmorillonite clay 19.2 (sold under the trade name 'Silton') Styrene butadiene latex binder 10.4 (sold under the trade name 'Dow 620') Fluorescent pigment granule mixture manufactured as described in Example I 0.1 : lO The other side of the paper was coated with 5 grams per square metre of a standard mix of microcapsules, starch . particles and carboxymethylcellulose as used in Example V.
: When the dried paper was observed under ultra-violet light, well distributed easily observed distinct spots were observed on both sides of the paper which fluoresced blue, yellow, orange and red and exhibited a good contrast against the background.
EXAMPLE VII
A mix was prepared according to the following formulation:-Grams Water 27.3 Kaolin (sold under the trade name 'Dinkie A' 26.8 Styrene butadiene latex binder10.8 (sold under the trade name 'Dow 620') Fluorescent pigment granule mixture manufactured as described in Example I 0.1 , ~279~
- l7 -Using a brush, a strip about 1 centimetre wide on each side of sheets of A4 size white paper of the kind used in Example V was coated with the formulation.
The paper was allowed to dry. Coating formulations of the kind specified in Example Vl were then prepared, except that the fluorescent pigment components were - omitted. The formulations were then applied to opposite sides of the paper sheet using the same coatweights as in Example V and dried. When observed under ultra-violet light, well distributed, easily observed distinct spots were observed on both sides of the paper in the zones where the brush coated strips had been applied which fluoresced blue, yellow, orange and red and exhibited a good contrast against the background.
:
.
The invention relates to identified paper for security and other purposes.
In many applications paper is required to be identifi-able as to source or authenticity as well as, in security applica-tions, difficult to counterfeit. Desirably also, attempts to falsify documents should irreversibly change the paper.
One approach has been -that of Aussedat Rey S.A. in their French Patent Application No. 80 06336 (2 ~78 695) laid open on September 25, 1981 in which luminescent particles are dispersed in the paper, showing up in ultraviolet light. Combinations of pig-ments can be used, as mixed agglomerates or added separately, and pigments sensitive to falsification procedures can be chosen.
There are however problems in insufficiently con-trolled incorpora-tion in the paper, losses on the machine, and obtrusiveness in ordinary use of the paper, as well as a wide variation in particle size.
We have studied the above approach and found that a key aspect is the particle size. Particles should neither be so large that they are distracting in the use of the paper, nor so small as not to be identifiable by eye when the paper is checked. Parti-cles that are too ,~
~279~8 '"
small merge into a general background and thus lose their identifying characteristics. Further, we have recognised that not only the predominant particle size but an absence of background from small particles, not S individually appreciable, is important if the quick checking of papers for source or authenticity that is necessary in practical use is to be achieved.
m e invention accordingly provides paper embodying for purposes of identification one or more pigments, inconspicuous in daylight but visible on inspection in darkened surroundings or after illumination at predetermined wavelength from an artificial source, wherein the pigment is in the form of granules which are of 30 to 500 microns, preferably 100 to 230 or 250 microns particle size and, to secure contrast between the pigment and backgr~und on said inspection, are essentially free of finer particles.
It is impracticable to quantify the limit for fine particles, but by careful production of the granules in the first place and by subs~quent sieving they can be reduced to a small proportion, certainly under 5% where the small particles of commercially available pigment are concerned and likely under 1~ by weight. The test is ; whether on inspection of the final paper there is contrast between a visually unreactive background and the granules. A paper according to the invention, ~LZ7~1S~3 - using fluorescent particles, can for example be viewed under ordinary room lighting by passing a U.V. lamp across it, when distinctive individual spots of light flash up against a background that, relative to them, is dark. Under similar c-,nditions a prior art product made without control of the granule size shows a diffuse and generalised reaction, uncontrolled and indistinct, against a background of light from individually indistinguishable particles.
The granules may for example be formed of a resin containing a light-reacting dye or of pre-formed light-reacting particles resin bonded, allowing close and pre-determined control of the particle size.
Such pre-formed pigment particles are conveniently themselves of a resin containing a light reacting dye, but there is no restriction to these and for example pigment materials light reactive per se, such as phosphorescent zinc sulphide particles, may be bonded~
~L279~5~3 An important subsidiary feature of the invention lies in a practical and convenient method of making the granules from commercially available pigments, which are supplied in very finely divided form. ~hus suitably the granules are formed by adding a quantity of a liquid resin binder to the particles and tumbling until aggregates constituting the granules have been formed, said quantity of binder being sufficient to aggregate the particles but not to form a continuous liquid phase.
In an important further embodiment, allowing far more particular characterisation of a paper, for example as to period as well as source of manufacture, the pre-formed particles are themselves of smaller particles~ preferably aggregated by a process as a~ove.
Desirably for security applications the granules are dispersed in the substance of the paper followiny incorporation in a paper-making stock, particularly immediately prior to the headbox. However, where identification rather than security as such is the important aspect, it is convenient if the granules are present as a coating or as separated indicia, applied to the paper.
Such indicia can be very economical of the pigments, a carbonless copy paper set for example needing only to carry, essentially only on one sheet of the set, sufficiently frequent indicia that one or more will appear on each quch sheet.
~27~ i8 Thus the granules may be in various forms, e.g.
aggregates of commercially available luminescent pigments used singly or to make mixed granules, or resins containing luminescent dye ground to form the granules, of granules of zinc or other phosphorescent compounds. It is also possible to use a combination of a resin, containing luminescent dye, acting as a binder for other pigments either in an aggregation process or in a direct process of formation of a block and grinding to size. The resin, or resin-bonded,granules are particularly suited to being incorporated in paper stock as they are not susceptible to size reduction in the paper-making process, partlcularly physical break-up in the refiners of the stock preparation system.
The luminescent material may be either fluorescent or phosphorescent. For example papex produced may be intended to be observed under U.V. light, particularly with the convenient battery operated low power U.V. sources now available for hand-held use, the particles fluorescing ` 20 in one or more colours. Each individual particle may show a single colour or a composite of two or more different colours. Paper may alternatively or in addition contain phosphorescent particles luminescing under the influence of daylight, and if such paper is observed in a darkened room, or a dark box, the sranules will continue to glow.
iL2~ i8 ~, In the aspect of the invention where resin-dissolved fluorescent dyes are used, suitable dyes and resins are known in themselves, available for example from Swada (London) Ltd., Sugar House Lane, London E.15 in their "Fiesta" (Trade M~lr]~) pigment range. The fluorescence of organic dyes is associated with the individual molecules of the dyes, and in order for them to fluoresce efficiently. they are molecularly dissolved in fairly low concentrations, for example from about 1 to 4%. ~s the dyes are organic in nature it is necessary to have an organic medium to take them into ~olution, and in order to have a pigment it is essential for medium to be solid. One type of material that meets these requirements is a melamine formaldehyde resin modified with sufficient aromatic sulphonamide to form a brittle thermoplastic or thermoset product which can be ground to the required particle size. Various red and orange shades are available with yellow, blue and green also.
The aggregation process descri~ed above was developed primarily because commercial luminescent pigments are generally available only in standard particle sizes of perhaps 3 to 5 microns. The agglomeration process generates particles of the larger size suited to the present use. However, luminescent pigments such as ~2~9~S~3 , the "Fiesta" range are in fact solutions of luminescent dyes in a base resin, and are made from block form by grinding. Where a single pic~ent is sufficient it can be made direct in the required size.
The question whether or not a mixed aggregate is necessary depends partly on uniqueness of identification, but also on the apparent colour of the particle required.
In cases where the required particle colour is that of one of the available luminescent dyes, one can simply use a particle of the right size ground from a block using such a dye. However, mixed apparent shades, for example greens not directly available, can be given by mixed aggregation of fine blue and yellow particles.
The invention thus conveniently uses:
- two or more luminescers, for ready exclusive identification - aggregates readily incorporated in papermaking and not degrading in size - particles convenient for ~bservation by reason of their size In a further aspect the invention provides a process of making pigment agglomerates, and the agglomerates produced, wherein pigments as ~bove are coated in reactive binder and formed directly or indirectly into the agglomerates. Preferably the coating is achieved by tumbling of pigment and binder and the tumbling continued ~7~58 until the desired agglomerates have formed. It is particularly advantageous to form sub-agglomerates of individual pigments in this way, and thencombine them into composite agglomerates. Highly characteristic paper can then be made, with the individual pigments in the agglomerates readily identified.
The tumbling is an essentially solid phase process operated with only sufficient liquid binder to coat the particles, but the use of a carrier solvent for theresin or other binder is not excluded. The agglomeration process can be closely controlled and the product graded, any undersize agglomerates being returned direct to the agglomeration process and any oversize product ground and likewise returned.
It will be appreciated that binder coating of the pigment may be achieved by other techniques. For example as referred to earlier herein, the pigment may be disposed in reactive binder and the binder cured to form a blck subsequentl~ ground to form the agglomerates.
Composite agglomerates if required are then made from separately made sub-ag~lomerates by a further agglomeration step.
In a particular process, pigment particles of 3 - 5~k~(micron) or other convenient particle size, are coated with a binder resin containing a cross linking -- 127~1S8 g catalyst, such as ammonium chloride. The binder can for example be a melamine formaldehyde or acrylic resin.
The particles are agglomerated by granulation in the solid phase as described above, to produce larger granules or agglomerates, and the binder is cured naturally or with heating, for example at 105C. The cured granules are sieved to exclude granules outside the desired particle si~e range and the sieved granules added to the paper machine prior to for~ing the web, e.g. in the pulper, chest or approach flow. Alternatively, sub-granules may be prepared from separate pigments, regranulated, and sieved to produce composite granules of two or more colours.
Granules produced in the ~id phase, by this granulation technique, comprise the 3 - 5 micron pigment particles chemically bound together by a fully cross linked binder. Prior agglomerates such as those of Aussedat Rey S.A. are formed in the liquid phase and, although a binder is present, this binder is not cross linked until the paper is dried on the paper machine. Such granules are physically, rather than chemically, agglomeratsd and it is impossible to control their production to a regular distrib~tion or to obtain in one paper different composite granules of two or more colours.
As to the stage of incorporation in the paper, success has been achieved by addition of the granules ~7~
to the thickstock contained in the chest of the paper machine priox to refining, to the refined thickstock in the second chest of the paper machine, and by addition to the size press. However, it has been found to be most beneficial to add the granules to the thinstock immediately prior to theheadbox to obtain the most desirable visual effect.
Particular examples of the use of the invention are as follows:
"Radglo" (Trade Mark~ pigments were used, obtained from Ciba-Gei~y and made by Radiant Colour ~.V.
Europarklaan B 3530 Houthalen, Holland. They comprised an aldehyde-sulfonomide-triazine polycondensation resin with fluorescent dyestuffs, known per se.
1 kg of each pigment powder, comprising particles in the range 3 to 5~ M diameter, was mixed in a stainless steel drum, rotating at 84 rpm and inclined at 30 degrees to the horizontal. An agitator positioned in the drum was rotated at 5000 rpm in the opposite direction to the rotating drum.
180 ml of an aqueous acrylic emulsion, "Acronal"
tTrade Mark) S 360 D, at 25% resin solids containing 0.5% ammonium chloride catalyst weight on resin solids was used. It was a styrene acrylonitrile and acrylic ester ~L2~79158 copolymer dispersion obtained from BASF (U.K.) Ltd., PØ
Box 4, Earl Road, Cheadlehume, Cheshire. An alternative catalyst is p-toluene sulphonic acid. The emulsion was slowly added to the fluorescent pigment powder which formed granules that increased in size as the emulsion was added.
The process was stopped before excessively large granules were formed.
It was noted that in this instance the temperature of the rotating drum had risen from ambient temperature to 30 C as the granulating process continued. It has however been found that the precise quantity of binder required differs from one batch to the next, depending partly on the skill of the operator but also on the : speed of addition, the temperature of the binder, the solids content and the chemical nature of the binder. For example, in a separate run it was found that 125 ml of a 35% solids solution of "Beetle BC 355" (Trade Mark) non-ionic methylated melami`ne formaldehyde resin binder, at 50 C, was sufficient. It was obtained from British Industrial Plastics, PØ Box 6, Pope's Lane, Oldbury, Warley, West Midlands.
The granules were removed from the drum and dried in an oven at 105 C (natural curing or microwave oYen heating are alternatives) for 1 hour to cross link 5 the binder, ar~ the size of the granules produced by the ~279158 .:
process was found to be very suitable at the high drum and agitator rotational speeds used.
The dried granules were sieved to remove granules smaller than 106~M andl~rger than 230 ~M. The small granules were regranulated and the large granules likewise retained for grinding, sieving and regranulation.
White (blue fluorescence), yellow, orange and red granules were produced by the granulation process.
The granules were mixed in the ratio of 4 : 3 : 2 : 2, by volume, and dispersed in water at a concentration of 1%
by weight. The dispersion of granules was pumped into the thinstock of a paper machine immediately prior to the headbox at the rate of 4 Kg granules/tonne paper (0.4 g/m2 on a paper of substance 100 g/m ).
When the paper produced by the addition of the granules was observed under ultra-violet light it was found to contain well distributed, easily observed distinct spots which fluoresced blue, yellow, orange and red~
EXAMPLE II
Two pigments corresponding to 3 - 5 ~M particle size pigments from the "Fiesta" range as referred to earlier herein, namely "Fire Orange A 4" and "Corona Magenta A 10", were prepared by dissolving the dyes (2% by weight~ in a standard aromatic sulphonamide-modified melamine forrhldehy~e resin hS used for 6uch pigrents, curing in - 1;2 79~L5~3 block form and grinding direct to 106 - 230~M Used in making of paper as in Example I these gave a security product with orange and red spots visible with care to the eye in daylight and orange and magenta fluorescence under wide-band U.V. light.
EXAMPLE III
500g of per se conventional fluorescent yellow pigment at 3 - 5 ~M particle size from the "Fiesta" range - was mixed in a rotating drum as in Example I. 150 ml of a polyvinyl acetate emulsion at 50~/O solids, "Vinamul"
R82020 (Trade Mark) was slowly added to the fluorescent pigment powder. It was a polyvinyl alcohol stabilised self cross linking polyvinyl alcohol emulsion obtained from Vinamul Ltd. at Mill Lane, Carshalton, Surrey. The process was stopped before the granules became excessively large. The granules were removed from the drum and allowed to dry at ambient temperature.
The granules were sieved to remove particles smaller than 106~ M and ~rger than 230~M.
Laboratory handsheets containing the granules were produced and were found to contain distinct spots which fluoresced yellow when observed under ultra-violet light.
~2~9~S8 EXAMPLE IV
Phosphorescent pigment 163G, a known zinc sulphide : copper activated pigment obtained from Derby Luminescents at Mill Marsh Lane, Brinsdown, Enfield, Middlesex was used, 25g cf the pigment being weighed into a laboratory beaker. 5g of a polyvinyl acetate emulsion, Vinamul R82020 (Trade Mark), at 50Y~ solids, was slowly added to the pigment and stirred vigorously with a glass rod to form granules.
The granules were removed from the beaker and allowed to dry at ambient temperature.
The dried granules were sieved to remove granules smaller than 106 ~M and larger than 230~ M.
Laboratory handsheets were produced containing the granules within the particle size range of 106~ M to 230~ M.
When thepaper, previously in daylight, was observed in a dark room it was found to contain well distributed easily observed distinct green sp~ts. It was found that the brightness of th~spots could be increased by prior exposure to ultra-violet light. The brightness of the spots was found to diminish with time if the paper was retained in the dark room without further exposure to ultra-violet or visible lignt.
EXAMPLE V
Using a laboratory coater, sheets of A4 size white paper of the kind used as a base paper in the manufacture of 'IDEM' (Registered Trade Mark) carbonless copying paper were coated on one side with 5 grams per square metre of a standard mix of microcapsules, starch particles and carboxymethylcellulose binder as used in such copying paper and in which had been dispersed 0.1% by weight of a fluorescent granule mix as described in Example I.
The other side of each sheet was similarly coated with 8 grams per square metre of a standard dispersion of acid washed montmorillonite clay (sold under the trade name 'Silton') and kaolin and to which 0.1% by weight of the same fluorescent granule mix had been added.
When the dIied paper was observed under ultra-violet light, well distributed easily observed distinct spots were observed on both sides of the paper which fluoresced blue, yellow, orange and red and exhibited a good contrast against the background.
EXAMPLE VI
Using a laboratory coater, sheets of A4 size white paper of the kind used as a base paper in the manufacture of 'IDEM' (Registered Trade Mark) carbonless copying paper were coated on one side with 8 grams per square metre of the following formulation:-~2~9~i8 Grams Water 27.1 Potassium hydroxide (50%) 0.6 Sodium hydroxide (30%) 1.3 Kaolin (sold under the trade name 'Dinkie A') 7.9 Acid washed montmorillonite clay 19.2 (sold under the trade name 'Silton') Styrene butadiene latex binder 10.4 (sold under the trade name 'Dow 620') Fluorescent pigment granule mixture manufactured as described in Example I 0.1 : lO The other side of the paper was coated with 5 grams per square metre of a standard mix of microcapsules, starch . particles and carboxymethylcellulose as used in Example V.
: When the dried paper was observed under ultra-violet light, well distributed easily observed distinct spots were observed on both sides of the paper which fluoresced blue, yellow, orange and red and exhibited a good contrast against the background.
EXAMPLE VII
A mix was prepared according to the following formulation:-Grams Water 27.3 Kaolin (sold under the trade name 'Dinkie A' 26.8 Styrene butadiene latex binder10.8 (sold under the trade name 'Dow 620') Fluorescent pigment granule mixture manufactured as described in Example I 0.1 , ~279~
- l7 -Using a brush, a strip about 1 centimetre wide on each side of sheets of A4 size white paper of the kind used in Example V was coated with the formulation.
The paper was allowed to dry. Coating formulations of the kind specified in Example Vl were then prepared, except that the fluorescent pigment components were - omitted. The formulations were then applied to opposite sides of the paper sheet using the same coatweights as in Example V and dried. When observed under ultra-violet light, well distributed, easily observed distinct spots were observed on both sides of the paper in the zones where the brush coated strips had been applied which fluoresced blue, yellow, orange and red and exhibited a good contrast against the background.
:
.
Claims (15)
1. Paper embodying for purpose of identification one or more pigments, inconspicuous in daylight but visible on inspection in darkened surroundings or after illumination at predetermined wavelength from an artificial source, wherein the pigment is in the form of granules which are of 30 to 500 microns particle size and, to secure contrast between the pigment and background in said inspection, are essentially free of finer particles.
2. Paper according to claim 1, wherein said particle size is 100 to 230 or 250 microns.
3. Paper according to claim 1, wherein the granules are formed of a resin containing a light-reacting dye or of preformed light-reacting particles resin bonded.
4. Paper according to claim 3, comprising the preformed particles, wherein the particles are themselves of a resin containing a light-reacting dye.
5. Paper according to claim 3, comprising the preformed particles, wherein the granules have been formed by adding a quantity of a liquid resin binder to the particules and tumbling unitl aggregates constituting the granules have been formed, said quantity of binder being sufficient to aggregate the particles but not to form a continuous liquid phase.
6. Paper according to claim 5, wherein the preformed particles are themselves aggregates formed by a like tumbling process.
7. Paper according to claim 1, 2 or 3, wherein the granules are dispersed in the substance of the paper following incorporation in a paper-making stock.
8. Paper according to claim 1, 2 or 3, wherein the granules are dispersed in the substance of the paper following incorporation in a paper-making stock but immediately prior to the headbox of a paper making machine.
9. Paper according to claim 1, 2 or 3, wherein the granules are present as a coating or as separated indicia, applied to the paper.
10. Carbonless copy paper sets wherein one or more sheets of the set constitute paper according to claim 1, 2 or 3.
11. Paper according to claim 4, comprising the preformed particles, wherein the granules have been formed by adding a quantity of a liquid resin binder to the particles and tumbling unitl aggregates constituting the granules have been formed, said quantity of binder being sufficient to aggregate the particles but not to form a continuous liquid phase.
12. Paper according to claim 11, wherein the preformed particles are themselves aggregates formed by a like tumbling process.
13. Paper according to claim 1, wherein the pigment is phosphorescent or fluorescent and is visible on illumination of ultraviolet light.
14. Paper according to claim 13, wherein said particle size is 100 to 230 or 250 microns.
15. Paper according to claim 13 or 14, wherein the granules are formed of a resin containing a light-reacting dye or of preformed light-reacting particles resin bonded.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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GB8529953 | 1985-12-05 | ||
GB858529953A GB8529953D0 (en) | 1985-12-05 | 1985-12-05 | Security paper |
GB868610993A GB8610993D0 (en) | 1986-05-06 | 1986-05-06 | Security paper |
GB8610993 | 1986-05-06 |
Publications (1)
Publication Number | Publication Date |
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CA1279158C true CA1279158C (en) | 1991-01-22 |
Family
ID=26290072
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Application Number | Title | Priority Date | Filing Date |
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CA 524500 Expired - Lifetime CA1279158C (en) | 1985-12-05 | 1986-12-04 | Security paper |
Country Status (9)
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US (1) | US4863783A (en) |
EP (1) | EP0226367B1 (en) |
AU (1) | AU594102B2 (en) |
CA (1) | CA1279158C (en) |
DE (1) | DE3669183D1 (en) |
DK (1) | DK167199B1 (en) |
ES (1) | ES2014990B3 (en) |
FI (1) | FI864951A (en) |
HK (1) | HK62390A (en) |
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US5045426A (en) * | 1989-06-21 | 1991-09-03 | The Standard Register Company | Toner adhesion-enhancing coating for security documents |
EP0453131A3 (en) * | 1990-04-12 | 1992-04-29 | James River Corporation | Security paper and method of manufacturing same |
US5234798A (en) * | 1991-10-04 | 1993-08-10 | Dittler Brothers, Incorporated | Thermal reactive structures |
US5289547A (en) * | 1991-12-06 | 1994-02-22 | Ppg Industries, Inc. | Authenticating method |
US5456498B1 (en) * | 1993-12-20 | 1998-03-10 | Edwin B Greene | Negotiable instrument fraud detector and processor |
DE4344552A1 (en) * | 1993-12-24 | 1995-06-29 | Giesecke & Devrient Gmbh | Method and device for equipping securities with authenticity features |
GB9522233D0 (en) * | 1995-10-31 | 1996-01-03 | Wiggins Teape Group The Limite | Pressure-sensitive copying paper |
US6106021A (en) * | 1998-02-02 | 2000-08-22 | Verify First Technologies, Inc. | Security papers with unique relief pattern |
US6045656A (en) * | 1998-12-21 | 2000-04-04 | Westvaco Corporation | Process for making and detecting anti-counterfeit paper |
JP3978961B2 (en) * | 1998-12-25 | 2007-09-19 | 特種製紙株式会社 | Fluorescent coloring particles used for anti-counterfeit paper, manufacturing method thereof, and anti-counterfeit paper using fluorescent coloring particles |
US6054021A (en) * | 1999-01-20 | 2000-04-25 | Westvaco Corporation | Process of manufacturing authenticatable paper products |
US6376135B2 (en) | 1999-05-11 | 2002-04-23 | The Standard Register Company | Image bonding treatment for retroreflective surfaces |
FI991438A (en) * | 1999-06-24 | 2000-12-25 | Neste Chemicals Oy | Organic pigment granulate for paper coating |
AU2001294172A1 (en) * | 2000-11-22 | 2002-06-03 | Tokushu Paper Mfg. Co., Ltd. | Particles emitting fluorescence by irradiation of infrared ray and forgery preventing paper using the same |
US20020066543A1 (en) * | 2000-12-05 | 2002-06-06 | Spectra Systems Corporation | Fluorescent micro-particles embedded in a pigmented fluorescent coating for optical document security |
GB0102876D0 (en) * | 2001-02-06 | 2001-03-21 | Secr Defence Brit | Triboluminescent devices |
DE10116315A1 (en) | 2001-04-02 | 2002-10-10 | Giesecke & Devrient Gmbh | Color coding for marking objects |
US20030211299A1 (en) * | 2001-09-27 | 2003-11-13 | 3M Innovative Properties Company | Adhesion-enhancing surfaces for marking materials |
US20030213841A1 (en) * | 2002-05-14 | 2003-11-20 | Josephson Stanley M. | Method for verifying and authenticating initially named payee of negotiable instruments |
DE10322841A1 (en) | 2003-05-19 | 2004-12-16 | Merck Patent Gmbh | Dual security feature |
US20050031838A1 (en) * | 2003-08-06 | 2005-02-10 | Spectra Systems Corporation | Taggant security system for paper products as a deterrent to counterfeiting |
US6916179B2 (en) * | 2003-08-28 | 2005-07-12 | Brenda Thornton | Kit for making rubbings |
FR2868093B1 (en) * | 2004-03-26 | 2007-07-13 | Honnorat Rech S & Services Sar | LAYER SAFETY PAPER |
EP2091750B1 (en) * | 2006-12-07 | 2010-03-10 | Agfa-Gevaert | Information carrier precursor and information carrier produced therewith. |
FR2970716B1 (en) | 2011-01-25 | 2013-09-06 | Honnorat Rech S & Services | SAFETY PAPER INFALSIFIABLE TO SOLVENTS |
FR2979358B1 (en) | 2011-08-31 | 2013-09-27 | Arjowiggins Security | INFORMATION SUPPORT FOR PRINTING ON LIQUID TONER PRESSES. |
DE102012013244A1 (en) * | 2012-07-03 | 2014-01-09 | Giesecke & Devrient Gmbh | Value document, method for checking the existence thereof and value document system |
FR2999617A1 (en) | 2012-12-18 | 2014-06-20 | Arjowiggins Security | INFORMATION SUPPORT FOR PRINTING ON OFFSET PRESSES. |
DE102013016121A1 (en) * | 2013-09-27 | 2015-04-02 | Giesecke & Devrient Gmbh | Value document and method for checking the existence of the same |
DE102013016134A1 (en) * | 2013-09-27 | 2015-04-02 | Giesecke & Devrient Gmbh | Value document and method for checking the existence of the same |
FR3030856B1 (en) | 2014-12-19 | 2018-02-02 | Arjobex | ADHESIVE LABEL |
DE102015014539A1 (en) | 2015-11-11 | 2017-05-11 | Giesecke & Devrient Gmbh | Security pigment based on core-shell particles and manufacturing process |
DE102015014526A1 (en) | 2015-11-11 | 2017-05-11 | Giesecke & Devrient Gmbh | A security pigment, a luminescent polymer resin and a process for producing the same |
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US3880706A (en) * | 1970-11-16 | 1975-04-29 | Harold Malcolm Gordon Williams | Security paper containing fused thermoplastic material distributed in a regular pattern |
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US3876496A (en) * | 1973-05-14 | 1975-04-08 | Ernesto B Lozano | Method and means for protecting documents |
DE2443164C2 (en) * | 1974-09-10 | 1976-09-02 | Hoechst Ag | THERMOPLASTIC PLASTIC FILM WITH RADIATION CHANGING PARTICLES |
FR2365656A1 (en) * | 1976-05-25 | 1978-04-21 | Arjomari Prioux | SECURITY PAPER |
US4166644A (en) * | 1977-06-21 | 1979-09-04 | Ncr Corporation | Pressure-sensitive record material containing urea-formaldehyde resin pigment |
FR2478695A1 (en) * | 1980-03-21 | 1981-09-25 | Aussedat Rey | Security paper incorporating dispersed luminescent particles - visible only in UV light, prepd. by adding particles suspension to finished pulp |
GB2122545B (en) * | 1982-06-26 | 1985-10-02 | Coated Papers Limited | Security paper |
EP0219743A1 (en) * | 1985-10-04 | 1987-04-29 | DeSoto, Inc. | Security paper containing vesiculated beads |
-
1986
- 1986-11-28 ES ES86309300T patent/ES2014990B3/en not_active Expired - Lifetime
- 1986-11-28 EP EP19860309300 patent/EP0226367B1/en not_active Expired - Lifetime
- 1986-11-28 DE DE8686309300T patent/DE3669183D1/en not_active Expired - Lifetime
- 1986-12-03 FI FI864951A patent/FI864951A/en not_active IP Right Cessation
- 1986-12-03 AU AU66045/86A patent/AU594102B2/en not_active Ceased
- 1986-12-04 DK DK583386A patent/DK167199B1/en not_active IP Right Cessation
- 1986-12-04 CA CA 524500 patent/CA1279158C/en not_active Expired - Lifetime
- 1986-12-05 US US06/938,439 patent/US4863783A/en not_active Expired - Lifetime
-
1990
- 1990-08-09 HK HK62390A patent/HK62390A/en not_active IP Right Cessation
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DK583386D0 (en) | 1986-12-04 |
DE3669183D1 (en) | 1990-04-05 |
DK167199B1 (en) | 1993-09-13 |
EP0226367A1 (en) | 1987-06-24 |
FI864951A0 (en) | 1986-12-03 |
ES2014990B3 (en) | 1990-08-01 |
US4863783A (en) | 1989-09-05 |
EP0226367B1 (en) | 1990-02-28 |
HK62390A (en) | 1990-08-17 |
AU6604586A (en) | 1987-06-11 |
DK583386A (en) | 1987-06-06 |
AU594102B2 (en) | 1990-03-01 |
FI864951A (en) | 1987-06-06 |
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