Composition of the paint including the optically changeable pigments, application of such composition, the optically- changed pigment and the method of treatment of such pigment

FIELD: chemical industry; printing industry; other industries; methods of production of the composition of the paint including the optically changeable pigments.

SUBSTANCE: the invention may be used in production of the optically changeable pigments. The optically changeable pigment includes the stratified set composed of the different materials, in which, at least, one of the layers represents the reflecting layer and, at least, one of the other layers represents the dielectric layer. At least, one of the surfaces of the indicated layers is subjected to the chemical action. The indicated materials also include, at least, one of the layers, which represents the semitransparent metallic layer made out of chromium and also one or more metals and-or their inorganic compounds. At that the metal and-or its inorganic compound are subject to corrosion. The subjected to the chemical action surface of the reflecting and dielectric layer along the edge of the layering block of the edge structure of the pigment is coated with the passivating agent, which is selected from the group consisting of the organic esters and the fluorinated organic esters of the phosphoric acid, having the following structural formula: (Rf-CH2-CH2-O)xP(O)(OH)y, where Rf=F-(CF2-CF2)z, х=1 or 2, у=2 or 1, х+у=3, z=l-7. The composition of the printing paint includes the binding system, water and the optically changeable pigment. The invention allows to diminish oxidation of the metallic layers and dissolution of the dielectric layers of the optically changeable pigment and to use it in the compositions of the printing paint.

EFFECT: the invention allows to diminish oxidation of the metallic layers and dissolution of the dielectric layers of the optically changeable pigment and to use it in the compositions of the printing paint.

22 cl, 7 ex

 

The invention relates to a passivated optically variable pigment, method for producing a passivated optically variable pigment, printing ink composition comprising the specified passivated optically variable pigment, the use of the composition of the printing ink, as well as to document with signs, printed the specified paint composition.

Paints containing optically variable pigment as a characteristic sign of the value of the document, widely used on banknotes and securities documents with the purpose of their protection against forgery using such conventional your color equipment, such as color copiers, scanners, and printers.

The level of technology

The basis of the optically changeable pigments conventional type is layered optical interference structure. The interference structure contains at least one metallic reflective layer, at least one transparent dielectric layer and at least one semi-transparent metal layer. As the metal reflecting layer use metals such as aluminum, gold, copper or silver, such chemical compounds as magnesium fluoride, silicon dioxide or aluminum oxide is used as the transparent dielectric layer, and metals such as chromium or Nickel are used as the e semi-transparent metal layer.

The incident white light is partially reflected from the pigmented translucent surface layer and partially from below the metal layer. Both parts of the reflected light pass through different optical path, depending on the wavelength leads to enhanced or weakened by the interference, i.e. for some wavelengths, the reflectance increases and the other decreases. This spectral selectivity is perceived by the human eye as the appearance of colors. For different angles of view, the difference in optical path is changed, resulting in color layered material changes depending on the angle of view.

Optically variable pigments are usually obtained by vacuum deposition of various required layers on a flexible grid. After applying the desired number of layers, the stack of layers is removed from the grid, dissolving it in a suitable solvent or removing the optically changeable material with mesh. After that, the optically variable material is crushed to the formation of scales, which are subjected to subsequent processing for adaptation to the desired application, for example, by milling, crushing, etc. the resulting product consists of flat scales with the broken edges with irregular shape and aspective ratio (aspect ratio). Such scales have two flat parallel surfaces is ti, having specified the interference properties.

The term "aspective attitude" (aspect ratio defines the relationship between the tensile flakes in a planar dimension and thickness of the interference layered system. The first of these values has a value of about 5-40 microns, while the second is usually 1 μm.

The basis of a practical embodiment of the scales of the optically variable pigment is symmetric system Cr/MgF2/AI/MgF2/Cr, in which the thickness of the absorbing layer of chromium is 3.5 nm, the thickness of the dielectric layers of the MgF2is 200-600 nm, and the thickness of the reflecting layer of aluminum is about 60 nm. The surface layers of chromium, among other things, provide effective protection of the lower layers of the MgF2and AI from chemical exposure.

However, in the field of violated edges of the inner layers of patterns available external influences and do not have any protective layer. For environmental reasons, it is now widely used and popular recipes aqueous printing inks. However, in the field of pH values, characteristic for water paints, it may corrode some materials optically variable pigment.

So, for example, formulations, printing inks containing aqueous acrylic emulsion, typically have a pH in the range 7.0-8.5 in. In these conditions the, chemical attack may be aluminum, especially in the presence of carboxylic groups and other chemical agents that form complexes with the ion AI3+. At the same time results in the release of hydrogen gas, leading to an expansion of the scaled interference patterns and disturbance of the optically variable color effect. Magnesium fluoride, which is the basis of the dielectric layers, are also soluble in water, which can lead to the destruction of the interference pigment and destruction of optically controlled color effect.

In patents US 5527848 and 5658976 describes passivation optically changeable pigments during processing of the pigment flakes salt solutions of transition and rare-earth metals, resulting on the surface of the pigment is formed a thin coating. In US patent 5545677, 5552458 and 5498781, as well as in EP 0688833 describes passivation optically changeable pigments by chemical modification reaction with a silanol functional group. These modified pigments used for preparation of the pigment formulations for coating.

The purpose of the present invention is to protect the optically modified pigments of the type specified above with the aim of reducing or inhibiting their oxidation metal layer and reduce or avoid dissolution of their dielectric is such layers. The chemical nature of the various materials of multilayer Cr/MgF2/AI/MgF2/Cr design specified optically variable pigment requires appropriate selection pestiviruses agent.

Another objective of the present invention is the use of such protective pigments in the composition of printing inks. A special target of the present invention relates to an aqueous formulation of inks for screen printing, containing piscivorous system for these optically changeable pigments.

The above and other objectives of the present invention are achieved in accordance with the independent claims.

Disclosure of the invention.

The composition of the printing inks of the present invention contains an organic binder system, water and a pigment selected from the group of interference pigments comprising a layered structure of different materials, in which at least one layer is a reflective layer, at least one surface exposed to chemical substances, and in which at least one other layer is a dielectric layer, at least one surface of which is subjected to chemical substances, and these materials contain one or more metals and/or inorganic metal compounds,moreover, the metal and/or inorganic derivative is sensitive to corrosion, and in which at least chemically exposed surface of the specified reflective and dielectric layer at the edges of the layer structure is covered by a significant number of pestiviruses agent chosen from the group of anionic detergents (tenside, surfactant).

Used in the text the term "tenside" refers to chemical compounds that combines two different types of chemical functionality, i.e. the hydrophobic part, the so-called "tail" of the detergent, which is soluble in solvents of low polarity (e.g., hydrocarbons), and polar hydrophilic part, the so-called "head" detergent), which are soluble in highly polar solvents (e.g. water). "Head" surfactants may incur a charge (anionic and cationogenic surfactant) or do not have a charge. In addition, surfactants can have more than one head and/or more than one tail.

Thus, the detergents can dissolve polar fragments in a nonpolar environment by assembling on the surface of the polar fragment, and the polar head detergent directed towards selection, and a nonpolar tail detergent facing the nonpolar environment. Similarly, the detergents can dissolve non-polar substances (e.g., grease) in a polar environment (for example, in the e).

The detergent may contain phosphorotioate group as "head" and the organic chain (e.g., hydrocarbon or fluorocarbon) as a "tail" or "tails". These tail group can join phosphoric acid in the esterification with the formation of phosphates. Phosphoric acid can provide up to three hydroxyl groups for esterification. In addition, the partially esterified phosphoric acid acts as a buffer with the participation of a certain number of protonated and deprotonated hydroxyl groups. This feature enables them to be used as pH regulators.

Hydroxyl group and the oxygen atom of the phosphate is able to function as complexing agents in relation to electrop ilen metal ions. The term "complexing" refers to electrostatic interaction between the nucleophilic ligand (hydroxyl group and/or the oxygen atom of phosphoric acid) and therefore electrophilic cation, as H+, Mg2+AI3+etc. resulting in chemical linking (joining) of the ligand to the cation. Attaching a ligand to the cation leads to the formation of molecular complex in which the cation is completely surrounded by ligands, or to the formation of the surface complex, in which Katie who is part of a solid surface (oxide, fluoride and the like) and the free surface side is occupied by one or more ligands.

Preferred pestiviruses agents for optically modified pigments of the above-mentioned type can be represented by a group of complex organic esters or fluorinated organic esters of phosphoric acid. Unexpectedly it was found that such esters of phosphoric acid (phosphates), which is a known, commercially available surface-active agents, have excellent connection capability for various optical materials modified pigments of the type Cr/MgF2/AI/MgF2/Cr.

In accordance with a preferred embodiment of the present invention the composition of the printing ink includes optically variable pigments, reflective layers are chosen from the group of metals, including AI, Fe, Ni, Cr, Zn. These metals have the properties required for obtaining optically changeable pigments, as well as excellent properties as a reflecting layer. It should be noted that the molecules mentioned phosphate detergents capable of firmly joining the ions of these metals with the participation of the phosphate "head" and, thus, protect (Passepartout) scales optically variable pigment from additional exposure reaktionstechnik him the ical substances from the environment (formulation of printing ink) using a hydrocarbon or fluorinated hydrocarbon "tails".

Passivation optically variable pigment can be done in two ways. In accordance with the first composition of the printing ink contains a passivating agent and the raw optically variable pigment directly added to the composition of the printing ink. However, in accordance with the second method it is also possible to pre-treat the optically variable pigment pestiviruses agent before introduction of the pigment in the printing ink composition.

In accordance with the present invention in both cases it was found that the addition of excess pestiviruses agent in the printing ink composition is advantageous, because in this case can provide protection for any fresh surface, which may receive, for example, during mixing.

In accordance with the present invention it is preferable that the printing ink composition comprised of optically variable pigments, dielectric layers are selected from the group of inorganic derivatives of metals consisting of MgF2, Fe2O3, Cr2About3, MgO, SiO2. It is established that metal cations such connections are firmly attached to the phosphate head groups of the detergent.

Thus, the present invention provides for use in a corrosive environment, for example, in the composition of the water is printing ink, corrosion-sensitive pigments with a high coefficient of reflection.

Particularly stable passivation is achieved in the case when the composition of the printing ink includes passivator selected from the group of organic esters and fluorinated organic esters of phosphoric acid, which meet the following General structural formula:

(Rf-CH2-CH2-O)xP(O)(OH)y,

where Rf=F-(CF2-CF2)z

x=1 or 2;

y=2 or 1;

x+y=3;

z=1-7.

The subscript x denotes the number of tails in the detergent molecule; the subscript y indicates the number of hydroxyl groups involved in the complex formation with metal ions. The sum of the indices x and y is always equal to three. The choice of the values of x and y defines the properties of the head group of the detergent. The subscript z denotes the number of fragments (CF2CF)attached to the link of CH2CH2O connecting the tail to the head group of the detergent. The choice of z determines the specific properties of the surface-active agent is related to its solubility in various solvents. It is established that the molecules of detergent above structural formulas, in which z has a value in the range from one to seven, have appropriate properties for the proposed use as pestiviruses agent for optically changeable pigments in prescriptions is ur ink.

In accordance with a preferred embodiment of the present invention the composition of the printing ink contains vesiviruses agent in the amount of 0.5-15 wt.% in the calculation of the mass of the optically variable pigment. A more preferred amount is 1.5 to 6.5 wt.% and even more preferably 2.5 to 5.0 wt.% in the calculation of the mass of the optically variable pigment. It is established that such amount pestiviruses agent sufficient for the application of pigments, at least a double layer of detergent molecules and, thus, able to effectively shielded metal or dielectric layers of pigment from the correlated action of the formulation of printing ink. Also found that similar amounts sufficient for immediate processing of optically variable pigment to cover its active surface with a clean, passivated optically variable pigment, designed for different applications.

Another aspect of the present invention relates to the composition of printing inks containing passivated optically variable pigment and having a pH value between 7.0 and 9.0. The preferred pH value of the composition of printing ink is 7.3 to 8.5, more preferably of 7.5 to 8.0. The selected pH value allows the use of smaller amounts pestiviruses agent with preservation of erosional resistance of the optically variable pigment and excellent properties of the composition of the ink before printing.

Another embodiment of the present invention relates to the composition of printing inks, in which the passivating agent is dissolved in an organic solvent. The use of dissolved pestiviruses agent provides improved readiness of detergent molecules to the coating on the optical surface modified pigments and improved floor surface.

In accordance with a preferred embodiment of the present invention, an organic solvent for dissolving pestiviruses agent in the composition of the printing ink selected from a group of simple glycol ethers or group of glycols. Such compounds provide excellent solubility of these surfactants.

Another aspect of the present invention relates to the composition of printing inks, including passivated optically variable pigment and a binder system containing an acrylic emulsion or urethaneacrylate copolymer, a crosslinking agent, an optional catalyst and optional additives. Emulsion acrylic or urethaneacrylate copolymer is chosen so that the emulsion was dissolved in an alkaline environment. This choice allows to obtain a stable composition of printing ink, without precipitation of the copolymer emulsion of composition.

In addition, the selected emulsion acrylic or urethaneacrylate copolymer who meet the value of T gin the temperature range -10°to+50°C. the Value of glass transition temperature Tgdefines the temperature range in which the condition of the emulsion changes from almost solid or highly viscous state (glassy state) to a state of low viscosity (liquid state). The inventors have found that the value of Tghas an important impact on the ability of the treatment composition of the ink during printing.

"Crosslinking agent" is a component contributing to the formation of a three-dimensional grid as a result of reaction with other components of the paint or other cross-linking molecules. In the context of the present invention, the term "curing" of "curing" refers to such drying, curing or polymerization of the printed ink after the printing process, in which the dye (i) is no longer able to be removed from the substrate and (ii) to adhere to other substrates above the printed ink. In addition, within certain limits, the curing passivates printed ink in relation to the different types of impacts (water, solvents, acids, bases and the like).

The term "vaccine" refers to a stable binding molecules of the crosslinking agent with the polymer molecules in the emulsion, acrylic and urethaneacrylate copolymer. Modified grafted m is likely have approximately the same physical properties, they had a reaction to vaccinations.

The term "catalyst" refers to a chemical compound, downward activation threshold of the chemical reaction of a certain type and, consequently stimulating the specified chemical reaction. The catalyst retains the same chemical composition before and after the reaction. In this regard, requires only small amounts of catalyst.

The term "additive" refers to compounds and materials that are used for regulating these physical and chemical parameters of the dye composition as pH, viscosity, texture, foaming, lubrication properties, etc.

In accordance with a preferred embodiment of the printing ink composition includes acrylic or urethaneacrylate copolymer emulsion binder system which is selected from the group of polymers having zameshivanii properties. These properties open the possibility of obtaining associated grid, which concluded pigment particles having high resistance to various kinds of chemical and physical effects.

Another preferred embodiment of the invention relates to a printing ink composition comprising a crosslinking agent, a binder system, which is chosen from the group of substituted alkoxysilanes (R1)y(R2O)zSi (R 1, R2represent different substituents, y+z=4), preferably from the group monosubstituted trialconsistent (y=1, z=3). The substituents R1, R2in the molecule of crosslinking agent include two different chemical functionality, the first of which, R1choose so that it reacts to print, and the second functionality, R2choose to effect the curing of the printed ink.

The first functionality enables the grafting of acrylic emulsion or urethaneacrylate copolymer cross-linking molecule that is able to react in the second stage, during initialization (the second function). This operation can be implemented in the short-term temperature increase, which triggers the secretion of protons by the decomposition of compounds, is introduced to neutralize the emulsion, and starts the sequence of stages of curing the printed ink film. The term "chemical functionality" means that a chemical compound contains a group of atoms that undergo reaction preferred specific type, for example, HE or SH group capable in the presence of a catalyst to interact with acids to form esters. Various chemical functional group is s (chemical functionality) are well known to the person skilled in the art. Using a special selection conditions (e.g. temperature, solvent and the like), the person skilled in the art can adjust the reaction of chemical compounds that contain more than one chemical functionality that the reaction will be to join just one of them.

According to another preferred embodiment of the composition of the printing inks of the invention, a crosslinking agent binding system selected from the group monosubstituted of triethoxysilane, preferably from the group epoxycycloheptane of triethoxysilane and group glycidylmethacrylate. Ethoxypropan as Deputy R2represents reaktsionnosposobnykh group capable of either hydrolyzed in controlled conditions and to react with other components of the formulation of printing ink or substrate. Epoxy fragment as Deputy R1capable of reacting with the functional groups of the acrylic emulsion or urethaneacrylate copolymer, creating a pre-formed grid to the printing process.

An additional aspect of the present invention relates to printing ink composition comprising a crosslinking agent in the amount of 0.25 to 3.0 wt.% calculated on the total weight of the composition. The preferred composition of the printing ink comprises a crosslinking agent in the amount of 0.5-2 wt.%, and even more preferred composition contains the crosslinking agent in the amount of 1-2 wt.%. It is established that these quantities provide sufficient resistance printed and utverzhdenii paint.

The preferred composition of the printing ink contains optically variable pigment in an amount of 10-25 wt.% by weight of the total composition. The preferred content of the optically variable pigment in the printing ink composition is 12-20 wt.%, even more preferably 15-18 wt.%. The specified number of optically variable pigment to provide a paint composition with excellent color coating and allow easy visual and/or machine detection optical properties of the printed and cured ink.

In accordance with the present invention are optically variable thin-film interference pigments, which are characterized by the fact that the surface of the pigment coated pestiviruses agent. Specified passivating agent selected from the group of anionic surfactants (detergents), and in accordance with the preferred embodiment of the groups of organic esters and fluorinated organic esters of phosphoric acid (phosphates). As noted above, the detergent basically acts as an intermediary between hydrophilic and hydrophobic components and can, for example, to dissolve the grease in the water or Vice versa. In addition to their surfactant is properties, the phosphate head group of the detergent is a good complexing agents and therefore able to join the ions of metals and surfaces containing metal ions.

Another aspect of the present invention relates to a method of passivation optically modified pigments comprising the following stages:

a) receiving pestiviruses agent or solution specified pestiviruses agent and its dissolution in an organic solvent,

b) adding water to the solution obtained in stage a) and thorough mixing of the resulting system;

c) establishing the pH of the composition is in the range of 7.3 to 8.5; preferably 7,5-8,0;

(d) dispersion of the optically variable pigment in the mixture obtained in stage (C).

Dissolution pestiviruses agent in an organic solvent and then adding water and establishment of pH provides reception detergent dispersed in the solution. Regulation of the pH before adding the optically variable pigment eliminates or reduces the likelihood of possible reactions of the acid form of the detergent with optically variable pigment. Consider the method allows to minimize the amount of detergent required for passivation of the surfaces of the optically variable pigment.

In accordance with a preferred embodiment of the invention, the way PA is sivali optically changeable pigments will include the use of pestiviruses agent in the amount of 0.5-15 wt.% calculated on the total weight of the optically variable pigment. A more preferred amount is 1.5 to 6.5 wt.%, even more preferably 2.5 to 5.0 wt.%. As noted above, these numbers provide a good coverage of the surface of the flake pigment.

Another aspect of the present invention relates to a method passivation optically changeable pigments, in which the organic solvent is chosen from the group of simple glycol ethers or group of glycols. It has been found that the solvents of this type provide a satisfactory solvation detergents.

Another aspect of the present invention relates to a method passivation optically changeable pigments, in which the pH value of the solution containing passivating agent, preferably set in the range of 7.3 to 8.5, more preferably of 7.5 to 8.0. It has been found that such values contribute a minimum number of correlated materials, such as phosphoric acid and hydroxyl ions in pestiviruses solution and, consequently, allow you to use the minimum number pestiviruses agent in relation to the number of optically variable pigment in ensuring the effective passivation.

Another aspect of the invention relates to the use of the composition of the printing ink containing the passivated optically variable pigments for screen, flexo and gravure water-based paints. Traditional methods such seals are typically associated with large amounts of organic solvents that are added to the paint in order to achieve low viscosity required for application, and which should evaporate after printing. Water paints based on polymer emulsions in water, and therefore eliminates the potentially dangerous effects to the health of workers, and in fact saved the environmental acceptability. Formulations of water-based paints almost incompatible with optically variable pigments, because of their very short shelf life due to degradation of the pigment. The present invention allows to form a water paint containing optically variable pigments having a shelf life comparable to the expiration date based paints solvent containing the same pigments.

Another aspect of the present invention relates to the marking of the document, obtained by means of silk screen, flexographic or gravure printing, the printing ink composition of the present invention. Marks containing passivated optically variable pigment, demonstrate excellent resistance to chemical and physical effects, compared with the same signs containing same, but the non-passivated optically variable pigment. Furthermore,signs, containing passivated optically variable pigment, have superior optical characteristics (as evidenced by the measured values of the color distortion and saturation) compared with marked, containing not passivated optically variable pigments. In addition, improved long light fastness of prints containing passivated optically variable pigment.

An additional aspect of the present invention refers to the document with the signs, the resulting printing ink of the present invention.

See below for further explanation of the present invention using examples related to the passivation of the optically changeable pigments and printing ink compositions, and the examples do not limit the scope of the invention and are merely illustrative in nature.

List of abbreviations:

- Imicure EMI-24 (Air Products) 2-ethyl-4-Mei

AMR-95 (Angus Chemie GmbH) 95% solution of 2-amino-2-methyl-1-propanol,

- DMA Fluca (N,N'-dimethylethanolamine)

- Neocryl XK-11 NeoResins/Avecia

- Neocryl XK-14 NeoResins/Avecia

- Neocryl BT-9 NeoResins/Avecia

- Neocryl BT-20 NeoResins/Avecia

- Armorez CR2900 Westvaco

- CoatOSil®1770 Witco Co. beta-(3,4-epoxycyclohexyl)ethyltriethoxysilane

- CoatOSil®H-11988 Witco Co. 40% emulsion CoatOSil®1770 input

- CX-100 NeoResins/Avecia derived polyaniline

- Zonyl® UR Dupont Fluoride p is supercial-active substance

Passivation optically changeable pigments

Optically variable pigments (OVP)used in the examples include 3 different material, a thin aluminum (AI) film, a dielectric layer made of magnesium fluoride (MgF2and a very thin layer of chromium (Cr). It is known that under alkaline conditions aluminum interacts with water in accordance with the following chemical equation:

2AI+6N2O+2HE-→2[AI(OH)4]-+3H2

In turn, magnesium fluoride, MgF2poorly soluble in water. Qualitative and quantitative analysis of water-soluble residue (Mg, AI, Cr) optically changeable pigments was performed by the method of atomic-absorption spectrometry, analytical method, well known to the person skilled in the art. The concentration of soluble Mg, AI, and Cr was measured in the supernatant obtained after dispersion of the optically variable pigment in water at pH of 8.5. Change the above concentrations was monitored for 2 months.

Example I

Direct passivation in the water.

1.4 g pestiviruses agent Zonyl®UR in acid form was dissolved in 10 ml of butyleneglycol. The resulting solution was diluted with deionized water to a volume of 100 ml. pH was determined using a DMA (N,N'-dimethylethanolamine). 5 g OVP was dispersible in 95 g of the above solution (Sample 1) at t=25°C. the Dispersion OVP filter is via 1 day 1, 2, 3 weeks and 2 months. The filtrate was diluted to 200 ml and analyzed by AAS method. For comparison purposes, the same procedure was performed using the non-passivated OVP (comparative sample 1).

The results of AAS analysis passivated and non-passivated OVP at different times stay in solution with a pH of 8.5.

t/days17142160
Passivated OVP (Sample 1)
Mg*3,03,54,04,06,0
AI*0,840,280,620,602,11
Cr*1,221,491,431,381,51
The non-passivated OVP (comparative sample 1)
Mg*24,027,025,027,031,5
AI*1,670,910,980,601,03
Cr*0,020,010,030,050,00
*: atomic concentration in ppm

Liability is the dominant agent reduces the concentration of Mg and AI at pH 8.5 compared with the non-passivated samples, except for the concentration of AI within 60 days of reaction. The concentration of Cr is higher than in the case of OVP, not passivated. Apparently, the passivating agent is a complexing agents and stabilisers Cr ions in solution.

Molecules pestiviruses agent samouporyadochennoi in the multilayer system and thereby create a hydrophobic barrier that prevents the penetration of water molecules on the surface of the OVP and hydration MgF2. It is assumed that the hydrolysis MgF2the water molecules occurs swelling of the dielectric layer, which is accompanied by deterioration or complete violation optical shift. Multilayer systems also allow you to eliminate the oxidation of AI under the action of hydroxyl ions.

Example II

0.5 g of Zonyl®UR was dissolved in 6 g of methyl ester of dipropyleneglycol and added 100 g of deionized water. AMR-95 was added to establish a pH value of 8.5 at 25°C. the resulting solution was dispersively 15 g OVP, with the color change in the range of green-blue (Sample 2). Prepared a comparative sample containing no pestiviruses additives at pH 8.5 (Comparative sample 2). After 24 hours, the dispersion was filtered, thoroughly washed with deionized water, but not dried, and the sample OVP re dispersible in solutions with the same pH value: 1, containing Zonyl®UR (sample 3) and 2, not containing Zony]&x000AE; UR (sample 4). Following the same methodology, 24 hours and 2 weeks method AAS measured concentrations of Mg, AI and Cr.

The results of AAS analysis sample 2 (S2), 3 (S3), 4 (S4) and comparative sample 2 (R2) at different reaction times.

Mg*/pH=8,5AI*/pH=10Cr*/pH=8,5
S2S3S4R2S2S3S4R2S2S3S4R2
1 day3,010,511,010,04,724,199,588,821,220,020,010,02
day 144,019,2519,015,04,222,091,561,01,430,040,020,03
*: atomic concentration in ppm

In the described method uses the ratio of Zonyl®UR to OVP green/blue, which is six times lower than in sample 1 which concentrations have different values.

Fine dispersion of the metal Cr in the ideal description of flakes or clusters, in the presence of pestiviruses agent acts as a very effective wetting and dispersing agent. These nanoparticles Cr contained in the "dust"generated during the operation of the seal in the production of OVP. Passivating agent removes the dust from the surface of the OVP and effectively distributes it in the water. The nanoparticles are too small, making filtering impossible. After filtering, OVP, wash and return to the previous state, in solution no longer detected the presence of Cr. Despite this concentration of Cr is very small [Cr]<1.5 h/million

Example III

Indirect passivation in nonaqueous solution

0.5 g of Zonyl®UR was dissolved in 6 g of methyl ester of dipropyleneglycol and 0.14 g AMR-95 was added to the system to neutralize passivator. The resulting solution was added to the OVP (15 g). Mixing was performed manually to ensure good wetting and the resulting mixture was stood for 24 hours. 7,22 g of a mixture containing 5 g of pure OVP, was added in aqueous solution (total amount: 100 g) at pH=8.5 and t=25°C. the resulting dispersion was filtered after 24 hours and 2 weeks, the volume of solution was brought up to 200 ml and the resulting system was analyzed by AAS method (Sample 5).

The results of AAS analysis of samples 1 (SI), and 5 (S5), and the comparative sample 1 (R1) at different reaction times.

Mg*/pH=8.5AI*/pH=10,0Cr*/pH 8,5
S1R1S5S1R1S5S1R1S5
1 day3,030,214,54,720,881,071,220,00,03
day 144,019,7518,254,220,421,221,430,00,03
*: atomic concentration, ppm

At the same concentration OVP and pH=8,5 initial concentration of Mg (14,5 h/m) has a significantly higher value after 24 hours than sample 1 (3 ppm), but it is significantly lower than in the comparative sample without passivation (30,2 ppm). Concentration Mg tend to align in 2 weeks (19,75 h/m).

Example IV

The effect of different concentrations of Zonyl®UR:

To 6 g of methyl ester of dipropyleneglycol was added 0, 0,1, 0,25, 0,5, 1 and 2 g of Zonyl®UR, setting the pH value to 8.5 using AMR-95. Then was added to the system water to obtain the mass of the solution is equal to 85, the resulting solution was dispersively 15 g ze is prohibited/blue OVP (sample 6) or 15 g purple/Golden Chromaflair® (sample 7). Passivated OVP or passivated Chromaflair® was filtered after 24 hours and 2 months, respectively, the obtained solutions brought up to a volume of 200 ml and analyzed by AAS method. Chromaflair® pigments were subjected to heat treatment in order to give stability to hydrolysis in severe weather conditions (development for the automotive industry).

The resulting concentration Mg for varying amounts Zonyl®UR at pH 8.5 and t=25°

0%0,1%0,25%0,5%1%2%
Sample 6
1 day24,06,03,52,02,54,0
60 days31,512,3210,33of 5.823,283,78
Sample 7
1 day9,53,11,11,62,24,1
60 days34,8823,889,716,52,133,78

As you can see from the data presented in the Table, the concentration of Mg depends on the concentration Zonyl®UR. primaluna concentration has a value in the range of 0.25 to 1%, in the ideal case of 0.5%. The ratio OVP/ Zonyl®UR should be maintained in the range of 1.5 to 6.5.

In the case of OVP, containing 0.5% Zonyl®UR, the concentration of Mg decreases to 12 times in 24 hours. After two months, the concentration of Mg increases, but still five times lower in the presence of 0.5% Zonyl®UR and eight times lower in the presence of 1% Zonyl®UR, compared with its absence.

As for Chromaflair®in the presence of 0.5% Zonyl®UR concentration Mg reduced 6 times in 24 hours. After two months, the concentration of Mg increases, but still 5 times less in the presence of 0.5% Zonyl®UR and 16 times lower in the presence of 1% Zonyl®UR, compared with its absence.

In the presence of Chromaflair pigment® the concentration of Mg two times lower than in the presence of pigment OVP.

Example V

One-component compositions of the aqueous printing ink containing passivated optically variable pigments, designed for rotary screen printing.

Water-based ink for screen printing with cetoscarus or optically variable pigment is applied on securities available-for printing banknotes using semi-automated gruntovalnoy machine (with rod device for coating No. 3, when the thickness of the wet film 24 μm). The paint is applied, dried for 30 seconds at 80°and using nail check is whether adhesion.

Determined chemical and physical resistance of the ink spreading under the influence of solvents, acids and alkalis at room and elevated temperatures, the creasing in the wet state (=WC) and in the dry state (=DC), and the abrasion resistance in wet (=WR) and dry (=DR), and were tested by washing (in accordance with rules established INTERPOL on 5thInternational Conference on Currency and Counterfeiting in 1969, or in accordance with the methods of the Bureau of Engraving and Printing's test according to BEP-88-214 (TN) section M5). Usually the most difficult to achieve resistance to washing, abrasion when wet and spreading when exposed to alkalis.

Tests on the creasing in the wet and dry States spend on IGT device. Print size is 5×5 cm fold and insert into the tube. Paper roll condense in the tube using a metal element with a diameter equal to the diameter of the tube. Processed paper smooth and rotate in the other direction (changing direction by 90°). After 4-fold repetition of the operation, the impression is turned on the other side. Operation is repeated 4 times in the wet state and 8 times in the dry state. Test in wet conditions is carried out in the same conditions with use of the imprint after moistening with water for 10 minutes.

Test abrasion was carried out on the device Prufbau. Conditions: trial n is abrasion in dry condition was performed 100 times using weight 610 g and test abrasion in wet conducted after moistening samples of water for 10 minutes.

The first test of washing called "stirring the solution for washing", was performed using a 1 l reactor, equipped with a mechanical stirrer, heating jacket, and containing 500 ml of water, 2.5 g of industrial detergent (Persil, Henkel or its equivalent) and 5 g of Na2CO3. In a reactor were placed three printed sample (in the form of squares of size 5×5 cm, counting to edge), the contents of the reactor were stirred and heated for 30 minutes. The samples were washed with distilled water and dried for 2 hours at 40°C. as a result used the average for the three samples. Slow mechanical agitation and high temperature used in this test illustrate the special chemical test.

The second test of washing, called "test in a washing machine", was performed using a standard washing machine (Lavamat W 1020, AEG) in the presence of 2 kg cotton fabric and 100 ml of detergent (Persil, Henkel). Printed samples (in the form of squares of size 5×5 cm, counting to edge) were placed in separate pockets cotton. Washing test was carried out for 40 minutes at 95°C. the Result was the average of the measurements for the three samples. Horo is its mixing in isolated pockets and high temperature illustrate the special physical test.

Change the paint was evaluated visually using the following scale:

ScoreVisual change colors
6Without changes
50-20%
420-33%
3Approximately 33-50%
250-66%
166-80%
080-100%

Samples 8 and 10 contain passivated optically variable pigments. Samples 9 and 11 contain the same pigments in non-passivated condition. The paint samples were prepared by the following procedure:

Sample 8.

1. In situ passivation of the pigment in the water.

Methyl ether of propylene glycol6,0
Zonyl UR0,5
Water22,0
OVP green/blue15,0
AMP-950,25

To a solution of Zonyl UR in the methyl ether of propylene glycol at 50°With added water. In addition, under conditions of agitation at room temperature and maintaining the pH in the range of 7.5 to 8.0 using AMR-95, added OVP. Pigment OVP slowly (500 rpm) was dispersively using a laboratory stirrer for 30 minutes.

Preparation of paint.

NeocrylXK-1148,0
Zonwax 223,0
Byk 024 (BYK-Chemie)1,9
Byk 025 (BYK-Chemie)0,1
Aerosil 200 (BYK-Chemie)1,0
CoatOSil 1770 Witco Co.1,0
Silwet L-7608 Witco Co.0,1

All the components were injected directly into the dispersion OVP and was stirred for 5 minutes at a speed of 1000-1500 rpm was Measured pH value and, if necessary, it was set in the range of 7.5 to 8.0 using AMR-95. With good stirring speed of 1500 rpm for 15 minutes in paint was added a mixture of CoatOSil® 1770 and Silwet L-7608.

2. Adjusting the viscosity.

Water1,7
Rheolat 2780,55

The system was carefully added thickener (Rheolat 278) to achieve a viscosity in the range of 250±50 MPa·C. If necessary, to maintain a pH in the range of 7.5 to 8.0, was added AMR-95.

The same paint was prepared without the use of passivator Zonyl UR (Sample 9). In the same way were prepared paint containing pigment Chromaflair™ (color change from purple to yellow), in the presence or absence of Zonyl UR (Samples 10 and 11).

p> The results of the test inks containing passivated and non-passivated optically variable pigments.

Sample 8Sample 9Sample 10Sample 11
MonthsLWM*LSS*LWM*LSS*LWM*LSS*LWM*LSS*
05,5of 5.754,5the 5.255,35the 5.254,3the 5.25
12,3the 5.73,75,55,25,64,35,3
215,52,3the 5.74,7554,15,5
* LWM: washing in a washing machine; LSS: washing solution + mixing

Example VI

The stability of the paint composition for rotary screen printing to the polymerization

After a certain period of time check the viscosity of the samples 8-11. Additional samples were prepared according to the method of example V except that at the stage of adjusting viscosity) of the paint composition was subjected to aging during the night (examples 12-15).

Days0714306090
25°
S8220735735835870980
S9250915850870930955
S10260490460480510615
S11250760725785850840
40°
S8220880900109015752540
S925041504525gelgelgel
S102606005457354695850
S112508408201660gelgel
25°0 day1 dayday 258 day84 day/td> 198 day
S12290365370435450755
S13265290300355360530
S14265310320320415700
S15290305340440430690

Gel = paint turns into a gel-like state and the viscosity measurement is impossible, the Stability of the color distortion

Samples of paint 12-15 kept at 25°and put on the paper for making money using semi-automated gruntovalnoy machine (with rod device for coating No. 3, speed 3). The first color was measured at an angle of 0° (specular angle) with lighting angle of 22.5°and the second color was measured at an angle of 67.5° when illuminated at an angle of 45° using a goniometer, specially designed for measuring the chromaticity of the optically changeable colors (Goniospectrometer Codec W-10 5&5 by Phyma GmbH. Austria). Has averaged five measurements at three different prints. Color values (L*, a*, b*, C*, h* and AE*) were recorded for each sample colors, and these values were recorded during the one hundred is to be placed. Hue h* OVI™ water-based ink for screen printing (color difference between the ink is printed after n days and paint, printed after its production) is more stable during aging using passivator than without it.

The results of measurement of hue h*

The first angle (0°)
Days01261322285684
S12117,23117,19116,99116,82115,98116,30116,07115,89116,55
S13116,83116,13116,07114,79114,81114,98114,74114,40114,80
S14313,97313,71313,33313,20312,55313,43131,06312,51313,45
S15131,19131,03312,24312,31311,21,312,25312,36311,06311,86
The second angle (67,5°
S12277,01276,92276,07276,34275,37275,54275,48274,90275,29
S13276,20275,71275,37274,19273,86273,87273,79is 273.16273,15
S14121,96121,97121,18121,03120,27120,81120,43120,01121,12
S15120,36120,29119,48119,32117,88118,53118,56116,97118,03

Example VII

Preparation of one-component water paints with passivated OVP for flat screen printing

Sample 16

1. Passivation of pigment in situ in the water.

Proglyde DMM6,0
Zonyl UR0,5
Water18,5
OVP green/blue15,0
AMR-950,25

Zonyl®UR was dissolved in Proglyde DMM (dimethyl ether of propylene glycol) at 50°and added water. At room temperature, and mixing conditions, obavljale OVP and using AMR-95 was established pH 7.5 to 8.0. OVP pigment was slowly dispersible in the system (500 rpm) using a laboratory stirrer for 30 minutes.

2. Preparation of paint.

Tegofoamex 8001,0
Jonwax 223,0
Neocryl BT-2050,0
AMR-951,0

Added antifoam and the wax and the mixture was stirred at a speed of 1000 rpm for 5 minutes. Then directly in OVP dispersion containing AMR-95, was introduced alkali-soluble acrylic emulsion Neocryl BT-20 and the resulting mixture was stirred with a speed of 1000-1500 rpm for 5 minutes to achieve a pH in the range of 7.5 to 8.0.

3. Adding a cross-linking agent.

CoatOSiI®17702,0
Silwet L-76080,2

The mixture CoatOSiI®1770 and Silwet L-7608 added into the paint with good stirring speed of 1500 rpm for 30 minutes. Before the correction, the viscosity of the paint, stood in for the night.

4. Viscosity correction.

Aerosil 2001,0
Water0,25
Acrysol RM-81,3
Only100

Was carefully added thickener (Acrsol RM-8) to obtain the viscosity of 800± 50 mPas If necessary, to maintain a pH in the range of 7.5 to 8.0, was added AMR-95.

The same paint was obtained in the absence of pestiviruses agent Zonyl®UR (Sample 17). Two identical paint formulations were prepared using the purple-green OVP pigment (Sample 18 containing Zonyl®UR, and the sample 19 without).

The prepared paint (Examples 16-19) kept at 25°and put on the paper for making money using semi-automated gruntovalnoy machine (with rod device for coating No. 3, speed 3). The first color was measured at an angle of 0° (specular angle) with lighting angle of 22.5°and the second color was measured at an angle of 67.5° when illuminated at an angle of 45. Has averaged five measurements at three different prints. Color values (L*, a*, b*, C*, h* and AE*) were recorded for each sample colors, and these values were recorded during aging. For example, ΔE* water-based ink for stencil printing, containing OVI™ (color difference between the ink is printed after n days and paint, printed after its production) is more stable during aging using passivator when both angles.

The measurement results ΔE*

1
The first angle (0°)
Days2571421285784
S161,821,940,961,721,201,541,092,271,67
S170,982,012,55to 2.673,293,12,69is 3.082,63
S180,530,191,291,481,231,992,031,991,36
S190,740,601,784,245,35the 5.455,615,996,79
The second angle (67,5°)
S160,890,662,132,222,013,331,742,132,14
S171,251,293,814,536,125,355,986,11to 5.93
S180,780,402,461,733,712,59/td> 3,93to 3.583,68
S191,220,852,08of 3.07of 3.644,554,785,70of 5.92

1. The composition of printing inks, including

a) a binder system;

b) water; and

c) a pigment selected from the group of interference pigments comprising a layered array of different materials, in which at least one layer is a reflective layer, at least one surface of which is exposed to chemical attack, and at least one other layer is a dielectric layer, one surface of which is exposed to chemical attack, where said materials include at least one of the layers, which is a semi-transparent metal layer of chromium, and also include one or more metals and/or their inorganic compounds, and metal and/or inorganic derivative susceptible to corrosion, and is exposed to the chemical effects of the reflecting surface and the dielectric layer at the edge layer of the array of regional patterns of pigment cover pestiviruses agent, and passivating agent selected from the group consisting of organic esters ftorirovannykh organic esters of phosphoric acid, having the structural formula

(Rf-CH2-CH2-O)xP(O)(OH)y,

where Rf=F-(CF2-CF2)z; x=1 or 2; y=2 or 1; x+y=3; z=1-7.

2. The composition of the printing ink according to claim 1, in which the reflective layers of the optically changeable pigments are selected from the group of metals, including AI, Fe, Ni, Cr, Zn.

3. The composition of the printing ink according to claim 1 or 2, in which the dielectric layers are optically changeable pigments are selected from the group of inorganic compounds of metals, including MgF2, Fe2About3, Cr2O2, MgO, SiO2.

4. The composition of the printing ink according to one of claim 1 or 3, containing passivating agent in the amount of 0.5-15 wt.%, preferably of 1.5 to 6.5 wt.%, and more preferably 2.5 to 5.0 wt.% in the calculation of the mass of the optically variable pigment.

5. The composition of the printing ink according to claim 1, in which the pH of the composition has a value of between 7.0 and 9.0, preferably of 7.3 to 8.5, and more preferably of 7.5 to 8.0.

6. The composition of the printing ink according to claim 1, in which the passivating agent is dissolved in an organic solvent.

7. The composition of the printing ink according to claim 1, in which the organic solvent is selected from the group consisting of simple glycol ethers or glycols.

8. The composition of the printing ink according to claim 1, in which the binder system further includes

(a) emulsion acrylic or urethaneacrylate copolymer;

(b) a crosslinking agent;

(c) an optional catalyst; and

(d) optional additional additives.

9. The composition of the printing ink of claim 8, in which the acrylic emulsion or urethaneacrylate copolymer, a subset of the binder system selected from the group of polymers having the property of clossiana.

10. The printing ink composition of claim 8 or 9, in which a crosslinking agent selected from the group consisting of monosubstituted of triethoxysilane, triethoxysilane, preferably from the group epoxycycloheptane of triethoxysilane and group glycidylmethacrylate.

11. The printing ink composition of claim 10, which contains 0.25-3 wt.%, preferably 0.5 to 2 wt.%, and more preferably 1-2 wt.% the specified crosslinking agent, calculated on the total weight of the composition.

12. The composition of the printing ink according to claim 11, which includes 10-25 wt.%, preferably 12-20 wt.%, and more preferably 15-18 wt.% optically modified pigment based on the total weight of the composition.

13. Optically variable pigment containing an array of planar layers, with the specified array of planar layers includes at least one reflecting layer and at least one dielectric layer having at least one surface exposed to chemical attack and susceptible to corrosion, which are susceptible to chemical who is actview the reflecting surface and the dielectric layer at the edge layer of the array of regional patterns of pigment cover pestiviruses agent, moreover, the specified agent selected from the group consisting of complex organic esters and complex fluorinated organic esters of phosphoric acid having the structural formula

(Rf-CH2-CH2-O)xF(O)(OH)y,

where Rf=F-(CF2-CF2)z; x=1 or 2; y=2 or 1; x+y=3; z=1-7.

14. Optically variable pigment in item 13, in which the number pestiviruses agent is 0.5-15 wt.%, preferably of 1.5 to 6.5 wt.%, and more preferably 2.5 to 5.0 wt.% calculated on the total weight of the optically variable pigment.

15. The processing method of optically variable pigment according to item 13 or 14, characterized in that it contains the following stages:

(a) receiving pestiviruses agent dissolved in an organic solvent;

(b) mixing water with the solution obtained in stage a);

(c) establishing the pH of the composition obtained in stage b), between 7.0 and 9.0; and

(d) diperkirakan optically variable pigment in the composition obtained in stage C), while maintaining the appropriate pH value of from 7.0 to 9.0.

16. The method according to item 15, wherein the specified number pestiviruses agent is 0.5-15 wt.%, preferably of 1.5 to 6.5 wt.%, and more preferably 2.5 to 5.0 wt.% calculated on the total weight of the optically variable pigment.

17. The method according to item 15 or 16, distinguishing the I, what organic solvent is chosen from the group of glycol ethers or glycols.

18. The method according to item 15, wherein the pH value is preferably set in the range of 7.3 to 8.5, and more preferably of 7.5 to 8.0.

19. Applying a printing ink composition according to claims 1 to 12 as a water-based ink for screen, flexo or gravure printing.

20. The marking of the document by the paint composition according to claims 1-12 method screen, flexographic or gravure printing.

21. The marking of the document, obtained by the method of screen -, flexo or gravure printing, a paint composition comprising optically variable pigment on PP and 14.

22. The document, labeled in accordance with PP and 21.



 

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2 tbl

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2 tbl

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2 tbl

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2 tbl

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