Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
  • C09C1/0021—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a core coated with only one layer having a high or low refractive index
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/50—Sympathetic, colour changing or similar inks
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
  • C01P2006/65—Chroma (C*)
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
  • C01P2006/66—Hue (H*)
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
  • C09C2200/10—Interference pigments characterized by the core material
  • C09C2200/1004—Interference pigments characterized by the core material the core comprising at least one inorganic oxide, e.g. Al2O3, TiO2 or SiO2
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
  • C09C2200/10—Interference pigments characterized by the core material
  • C09C2200/1004—Interference pigments characterized by the core material the core comprising at least one inorganic oxide, e.g. Al2O3, TiO2 or SiO2
  • C09C2200/1008—Interference pigments characterized by the core material the core comprising at least one inorganic oxide, e.g. Al2O3, TiO2 or SiO2 comprising at least one metal layer adjacent to the core material, e.g. core-M or M-core-M
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
  • C09C2200/10—Interference pigments characterized by the core material
  • C09C2200/1054—Interference pigments characterized by the core material the core consisting of a metal
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C2220/00—Methods of preparing the interference pigments
  • C09C2220/10—Wet methods, e.g. co-precipitation
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C2220/00—Methods of preparing the interference pigments
  • C09C2220/20—PVD, CVD methods or coating in a gas-phase using a fluidized bed

Definitions

• Ink composition comprising first and second optically variable pigments
• This invention relates to a printing ink composition
• a printing ink composition comprising first and second multi-layered thin-film interference pigments showing a colour shift which depends on the viewing angle.
• Pigments consisting of thin multi-layered film interference structures which show a viewing-angle dependent shift of colour have been described in various publications as, for example, L. Schmid, M. Mronga, V. Radtke, 0. Seeger "Luster pigments with optically variable properties", European Coatings Journal, 7-8/1997, and patents, e.g. US 4,434,010, US 5,059,245, US 5,084,351, US 5,281,480.
• OVP Optically Variable Pigments
• PVD Physical vapour deposition
• the method consists in forming a multi- layered, thin film coating by advanced PVD techniques such as roll coaters, sputtering techniques, etc. on a flexible web of a material, which is preferably soluble in a predetermined solvent.
• the web is typically a polymer material, such as polyvinyl alcohol or polyethyleneterephthalate .
• flakes are produced therefrom by shredding or grinding them down to the desired flake size.
• the separation can be accomplished by stripping the multi-layered coating from the web. For this, preferably a stripping layer is deposited onto the web prior to the other layers . Heat and/or solvent may be used to facilitate the stripping process.
• the web may be dissolved in a suitable solvent to accomplish the separation.
• the coated web may optionally be cut or shredded prior to the dissolution step.
• the multi- layered thin film coating is separated from the web, it typically breaks into pieces of irregular shapes and sizes. These pieces usually require further processing to achieve the desired flake size which is suitable for use as pigment flakes in coating compositions and particularly ink compositions.
• the flakes can be ground down to a size ranging from 2-5 microns without destroying their colour characteristics. Preferably the average particle size is between 5 and 40 microns, but not greater than 120 microns.
• the flakes are produced to have an aspect ratio of at least 2:1.
• the aspect ratio is ascertained by taking the ratio of the largest dimension of a surface of the flake parallel to the planes of the layers to the thickness dimension to the flake (perpendicular to the plane) .
• the flakes can be achieved by all major categories of processing known in the art such as milling, grinding or ultrasonic agitation, optionally in the presence of solvents and/or further auxiliary materials.
• OVP produced by this production process are characterized in that the pigment flakes consist of a stack of plane layers lying parallel to each other with outer pigment flake surfaces parallel to each plane layer. Due to the shredding and grinding process, the surfaces of the pigment flake perpendicular to the plane of the layers are irregularly formed with the inner layers not covered by the outer layers .
• OVP having these characteristics will be referred to hereinafter as OVP A.
• the plate-like pigments are suspended in an alcohol with dispersion aids. Tetraethoxysilane and an aqueous solution of ammonia is continuously added to this solution. Under these conditions, tetraethoxysilane is hydrolysed and the resulting hydrolysis product, the hypothetical silicic acid Si(0H) 4 , condenses and forms Si0 2 as a smooth film on the surfaces of the plate-like pigments.
• the Si0 2 - coating can also be carried out in a fluidized-bed reactor. In this case, vapours of tetraethoxysilane must react with water vapour. However, at the preferred temperatures of the gas-phase deposition
• tetraethoxysilane does not react in satisfactory yields.
• Special precursors, which are more reactive have to be used. Suitable precursors are of Si (0R) 2 (OOCR) 2 -type. They vaporize at 150°C and decompose easily with water at 200°C.
• the silicon oxide-coated pigments are coated with metal oxides or metal films .
• the coating takes place in a fluidized-bed reactor.
• the Si0 2 coated pigments are fluidized with inert gases, which are charged with gaseous metal carbonyls. At 200°C the carbonyls decompose. If iron carbonyl is used, it can be oxidized to Fe 2 0 3 , which forms smooth thin films on the pigment surfaces.
• the iron oxide coating can be carried out in a sol-gel technique known from conventional micas .
• OVP produced by this process possess just one coherent surface.
• the outer coatings surround and encompass inner coatings and/or the reflective core flake. Because of this, the outer layers are not planes, but are substantially parallel to each other.
• the outer pigment surface is not continuously parallel to the first and second surface of the plate-like reflecting pigment. OVP showing these shape characteristics will be referred to hereinafter as OVP B.
• OVP includes a totally reflecting layer of a material which in the majority of cases is a metal such as aluminium, gold, copper or silver or a metal-oxide or even non-metallic materials.
• the first reflecting layer has a suitable thickness in the range of 50- 150nm but can be up to 300 nm.
• Deposited onto the totally reflecting material is a material with a low-refractive index; such material is often called dielectric material.
• This layer of a dielectric material must be transparent, with a refraction index not higher than 1.65.
• Si0 2 or MgF 2 are the preferred dielectric materials.
• the subsequent semi- opaque layer or layers are of a metal, metal oxides or sulphids as, for example, aluminium, chromium, MoS 2 or Fe 2 0 3 .
• Opaqueness of metal is a function of the layer thickness . Aluminium, for example, becomes opaque at approximately 35 to 40 nanometers. Typically the thickness of the semi-opaque layer is between 5 to 10 nanometers. The thickness of the dielectric layer depends on the colour desired. It is thicker if longer wave-lengths are required.
• OVPA can be of a symmetrical or asymmetrical multilayered structure with regard to the totally reflecting layer.
• Hue angle h arctg(a*/b*) is 0° along the +a*-axis, 90° along the +b*-axis, 180° along the -a*-axis, 270° along the -b*-axis and 360° (same as 0°) along the +a*-axis(see R ⁇ mpp Chemie Lexikon, "Lacke und Druckmaschine” , Ed. U. Zorll, Georg Thieme Verlag Stuttgart, New York 1998) .
• the flatness of the OVP A flakes allow a parallel orientation both to the underlying substrate and to each other when incorporated in an ink composition and printed.
• the therewith coated surface presents in consequence almost ideal reflecting conditions at the characteristic wavelengths of the OVP.
• flake characteristics which are the result of the PVD production process (plane-parallel layers, absolutely plane and smooth surfaces of the individual layers, minimal deviation of layer thicknesses compared to the predetermined and desired value)
• chroma color saturation
• Due to large amount of colour shift OVP A has found wide application in copy-preventing applications for security documents such as banknotes, checks, credit cards, passports, identity cards, driving licenses, postage stamps etc.
• OVP-A can be blended with conventional colored or black pigments to attain this and other, related goals (cf. "Counterfeit deterrent features for the next-generation currency design", Publication NMAB-472, National Academy Press, Washington, 1993, pp 55-58, and references cited herein) . However the mixture with black result in a dull and covered colour.
• Another method consists in blending OVP-A with suitable mica pigments, whereby the shade of the mica pigment is chosen to be similar to either the normal view color or the grazing view color of the OVP-A in question.
• the second color of the OVP is strongly perturbed in such mixtures, leading to an unsatisfactorily small color shift which is sometimes not even perceptible for the human eye. Therefore the mixture is unsuitable for anti-counterfeiting applications .
• OVP A is expensive due to the costly production machines and process .
• OVP B is cheaper, however the colour shift of coating composition comprising OVP B is weak, sometimes not even perceptible to the human eye, e.g. when shifting within one shade, eg. red. Therefore printing inks comprising OVP B are not suitable for copying preventing applications on security documents.
• an ink composition comprising a polymer resin binder and first optically variable dichroic pigment flakes consisting of a comminuted multi-layered thin film interference structure comprising a stack of entirely parallel and plane layers in which at least one of the layers is totally reflecting, having first and second plane surfaces parallel to each other, and deposited on at least one of the plane surfaces at least one transparent dielectric layer, the ink composition further comprises second optically variable multi-layered thin film dichroic pigments comprising a reflecting plate-like core layer in which the reflecting core layer is completely enclosed by at least one transparent dielectric layer and/or semi-opaque metal or metal-oxide layer.
• the first and second optically variable dichroic pigments are selected such that they are not antagonistic to each other.
• “Antagonistic" in the CIELAB colour-measuring system means that the shades (chroma + hue) of both of the orthogonal and of the grazing view of the first and the second optically variable dichroic pigment are related by a center of inversion.
• OVP-blending follows the rules for additive color mixing, i.e. blending red and green OVP yields yellow. Subtractive color mixing, using red and green conventional pigments, would yield black. For this reason, mixing OVP pairs with partly " antagonistic" properties (i.e. having either complementary colors, or counter-acting color shifts) can yield very interesting results.
• OVP A By blending OVP A and OVP B a reduction of chroma of OVP A is achieved. Beside the reduction of the chroma of OVP A, it has unexpectedly been found that a blend of these two types of OVP maintains a clear colour shift between two distinct shades (perceivable by the human eye), e.g. green to blue, margenta to green even when OVP B quantitatively dominates in the blend. This makes the OVP-blend suited for security applications.
• the chroma C* (orthogonal view) of the first optically variable dichroic pigment is equal or above 50, more preferably equal or above 55 and even more preferably equal or above 60, whereas the chroma C* (orthogonal view) of the second optically variable pigment is below 50 preferably below 40 and even more preferably below 30.
• An unexpected synergistic effect is the improvement of the chemical resistance of the cured ink layer even if the amount of pigments of OVP A exceed the amount of OVP B.
• the chemical resistance of cured ink layers comprising blends of OVP A and OVP B instead of just OVP A is particularly strengthened against 2% caustic soda solution, sodium sulphide and industrial laundry.
• a preferred embodiment of the present invention is an ink composition
• a polymer resin binder and first optically variable thin film dichroic pigment flakes consisting of a comminuted multi-layered thin film interference structure comprising a stack of parallel and plane layers in which at least one of the layers is of a reflecting material having first and second plane surfaces parallel to each other and disposed on at least one of the plane surfaces at least one transparent dielectric layer, the ink composition further comprising second optically variable thin film dichroic pigments comprising a reflecting platelike core layer which is completely enclosed by at least one transparent dielectric layer and/or a semi-transparent metal or metal-oxide layer whereby the two dichroic hues of the first and second optically variable, thin film, dichroic pigment flakes are substantially the same.
• the first thin film multi-layered interference structure corresponds to OVP A and the second multi-layered interference structure corresponds to OVP B.
• red is any transmitted or reflected colour of a wavelength of between about 610 and about 700 nm; orange is any transmitted and reflected colour of between about 590 and 610 nm; yellow is any transmitted or reflected colour of between about 570 and 590 nm; green is any transmitted and reflected colour between about 500 and about 570 nm; blue is any transmitted or reflected colour of between about 460 and about 500 nm,- and violet or purple is any transmitted colour of between about 400 and about 460 nm.
• substantially the same hues means that the hues designated by values of a* and b* are not differing more than 60 degrees from each other on the CIELAB colour-measuring system.
• the first multi- layered thin film interference structure (OVP A) has a symmetric construction in respect to the first reflecting layer.
• at least one transparent dielectric layer with an index of refraction not higher than 1.65 is deposited in such a way that the resulting dielectric layers are plane and parallel to the surface of the reflecting layer.
• the visual effects of the first multi-layered thin film interference structure, OVP A, is enhanced when a semi-opaque metal or metal-oxide layer is deposited on at least one of the dielectric layers.
• OVP B the second multi-layered thin film interference structure, OVP B, in case the dielectric layer is surrounded by a semi-opaque metal or metal-oxide layer.
• Preferred materials for both multi-layered interference structures are chromium for the semi-opaque layer and aluminium for the reflecting layer.
• the blend ratio of the first and second multi-layered thin film interference structure should be in a ratio of 1:10 to 10:1, preferably in a ratio of 1:1.5 to 1:0.6.
• the ink composition of the present invention may further comprise additional non-interference pigments.
• Blends of OVP A and OVP B can be incorporated in any suitable ink vehicle as long as the ink vehicle is not detrimental to the visual appearance of the OVP. Particularly it must not cover the optical effects of the pigment and must not be aggressive to the layer materials .
• ink vehicles comprise at least one film-forming polymeric binder, solvents, optionally water, extenders and auxiliary agents such as non-foaming-, wetting-, rheology-control agents, antioxidants, etc.
• the ink layer can be applied to the underlying substrate by any of the known printing techniques, in particular by intaglio, flexographic, gravure and silk-screen printing.
• An ink composition comprising first and second multi-layered interference structures is preferably used for printing security documents such as bank notes, cheques, credit cards, etc.
• security documents such as bank notes, cheques, credit cards, etc.
• the colour shifting properties of an image printed by using such an ink composition are not reproducible by photocopying and as such impart to the document a strong security feature.
• an ink of the kind described by the present ⁇ 2 is preferably used for printing security documents such as bank notes, cheques, credit cards, etc.
• OVP-A magenta-to-green (M/G) , green-to-blue (G/B) and blue-to-red (B/R)
• M/G mangaenta-to-green
• G/B green-to-blue
• B/R blue-to-red
• Blends visual effects (color shift) under daylight
• OVP blends with partially antagonistic behavior of the constituents showed, surprisingly, striking color shifts, too, as the blend of ED 1821 with G/B (changing from green to almost black) or the blend of ED 1821 with B/R (changing from violet to brown) .
• a silk screen printing ink was produced by incorporating various percentages of OVP-A and/or OVP-B into a suitable ink matrix.
• the corresponding chroma and colour (hue) values h were measured on a printed and cured ink patch (silk screen prints made with a Hand Coater no .3 ; measurements performed on a PHYMA Penta Gonio PG-5 instrument, using illumination/detection angles with respect to the normal of 22.5°/0° for orthogonal view, and of 45.0°/67.5° for grazing view), and are given as a function of the blend composition in Tables la to lg and in the corresponding Figures la to lg and Fig.2.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Composite Materials (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)
• Ink Jet Recording Methods And Recording Media Thereof (AREA)
• Laminated Bodies (AREA)
• Paints Or Removers (AREA)
• Pigments, Carbon Blacks, Or Wood Stains (AREA)
• Liquid Crystal Substances (AREA)
• Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
• Printing Methods (AREA)
• Credit Cards Or The Like (AREA)

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