Aqueous dye for stenciling, method for its preparing and using

FIELD: dyes.

SUBSTANCE: invention relates to composition of aqueous dye used in stenciling, to a method for preparing indicated composition of stenciling, using indicated dying composition for stenciling and to securities printed using indicated dying composition. Invention describes composition of aqueous dye for stenciling containing the following components: (a) emulsion of acrylic or urethane-acrylic copolymer taken in the amount 30-70 wt-%, preferably in the amount 35-60 wt.-%, and more preferably in the amount 40-55 wt.-% of self-cross-linking emulsion of acrylic or urethane-acrylic copolymer as measured for the total mass of composition; (b) cross-linking agent taken in the amount 0.25-3 wt.-%, preferably in the amount 0.5-2 wt.-%, and more preferably in the amount 1-2 wt.-% of mass indicated cross-linking agent as measured for the total mass of composition; (c) optional catalyst; (d) optional pigments, and (e) optional additives and wherein indicated cross-linking agent comprises at least two different functional activity in a single molecule. The first functional activity is chosen by so manner to form a covalent bond with indicated polymer before printing and the second of indicated functional activities is chosen by so manner to carry out cross-linking indicated polymer for hardening printed dye. Emulsion of acrylic or urethane-acrylic copolymer is chosen from group possessing self-cross-linking property and wherein the composition shows pH from 7.0 to 8.5, preferably from 7.5 to 8.3 and more preferably from 7.5 to 8.0. Invention describes a method for preparing above said composition of aqueous dye for stenciling and comprising the following steps: (a) preparing emulsion of acrylic or urethane-acrylic copolymer; (b) optional preparing catalyst, optional pigments and optional additives; (c) preparing a cross-linking agent able to form a covalent bond under the first conditions with polymer prepared in (a), and cross-linking prepared polymer under the second conditions; (d) thorough mixing components prepared by points (a), (b) and (c) and providing interaction of polymer prepared by point (a) with a cross-linking agent prepared by point (c) under indicated first conditions; (e) regulation of pH value of the composition in the range from 7.0 to 8.5. Also, invention describes using the indicated composition of aqueous dye as a dye for stenciling and security document with signs printed by using indicated composition of aqueous dye. Proposed composition shows improved stability and improved toxicological properties in the combination and excellent stability of printed and hardened dye to chemical and physical effects.

EFFECT: improved properties of dye, improved preparing method.

14 cl, 6 ex

 

The technical field to which the invention relates.

The present invention relates to the composition of water-based ink for screen printing, the method of obtaining the specified composition of the printing ink, the application of the above dye composition for screen printing, as well as valuable documents printed using the dye composition.

The level of technology

Printed valuable documents, such as banknotes or other valuable documents, must be resistant to physical and chemical effects of the environment (Interpol Resolution No. AGN/67/RES/11 of 67thSession - Cairo, 1998; Interpol Resolution No. 8 of the 5thInternational Conference on Currency Counterfeiting - Mexico, 1969). According to the prior art, to perform such strict sustainability requirements of gravure, letterpress or offset inks are special lacquer formulations.

In regard to the use of special pigments, such as known in the field of optically modified pigments of different types, iridescent pigments or other pigments with optical effect, the last time for printing important documents used screen printing as the most appropriate application of these pigments. Must be received by this ink for screen printing, which, on the one hand, satisfies the requirements of industrial equipment is for screen printing, on the other hand, has the necessary resistance to external influences.

Industrial screen printing is carried out on rotary printing machines or ink machines. Because the printing process such equipment runs at high speed (5000-12000 pages/hour or 100-150 m/min), the relevant stage of such printing processes is the stage of drying. In the processes of rotary screen printing you want to use a different type of dye composition than in the process of screen printing ink on the machines, which is mainly due to different methods of ink in the printing process. In accordance with this formulation of the ink must be adjusted or selected in accordance with the terms and conditions printed on different presses. Based on the environmental requirements and considerations related to safety and health effects on staff, it is preferable to use aqueous formulations of inks for screen printing, and not compositions containing volatile organic solvents.

In accordance with the prior art to achieve a desired resistance to chemical and physical effects typically use a two-component (2C) water paint. For preparation of such inks for screen printing use solutions or emulsions (water is abbasseya emulsion acrylic or polyurethane resins. To achieve the required stability before printing system always add a crosslinking agent (in an amount of 0.5-3%). In aqueous formulations typically use a universal and well-known cross-linking agent (amendment, "crosslinker") CX-100 from NeoResins/Avecia (formerly Zeneca). Excellent results were obtained when adding before printing 1% CX-100 in the ink for screen printing on rotary printing machines (6/6 in tests with washing after only 2 days). In addition, the use of CX-100 in aqueous ink for screen printing is a common procedure.

CX-100 is polisilicon, and reported its toxicity. There are obvious disadvantages relating to the use of such a cross-linking agent in water based inks for screen printing banknotes: this substance should be added immediately before printing and it should be added in exactly the required amounts in order to avoid receiving the defective prints.

Additional disadvantages of polyaniline as a cross-linking agent can be attributed to the fact that he is able to modify the viscosity of the paint only after you add and what its life in aquatic systems is limited to 6-8 hours. Re-add polyaniline in the paint can in 2-3 days lead to zeresenay.

There is an obvious need to create a one-component, ready-to-print coloring the it system, with indicators related to resistance to chemical and physical influences, and rate of solidification, are similar to those of two-component printing ink.

In EP 597986 describes the formulation of water-based ink for screen printing, comprising of acrylic emulsion and/or a polyurethane dispersion as binder system, together with pigments and optional additional additives in the usual concentrations, known to the person skilled in the art. Describes the formulation of the ink is optimized for use in the process of screen printing, in which the screen grid is placed in a closed housing to maintain it constant humidity in the printing process.

Disclosure of inventions

The purpose of the present invention is to develop a one-component water-based ink for stencil printing, having a more convenient chemical composition, improved stability, and improved Toxicological properties in combination with excellent resistance printed and cured ink to chemical and physical influences.

This and other goals have been achieved using the present invention in accordance with the independent claims.

The water-based ink composition includes a binder system selected from the group consisting of acrylic emulsions or urethaneacrylate is polimerov, cross-linking agent, an optional catalyst, pigment, and optional additives. A crosslinking agent contains at least two different functional groups, the first of which is designed to respond before printing, and the second functional group is chosen in such a way as to carry out the curing of the printed ink. Specified acrylic or urethaneacrylate copolymer emulsion is chosen from the group of emulsions with zameshivanii properties.

The first functionality enables the grafting of acrylic emulsion or urethaneacrylate copolymer cross-linking molecule that is able to react on the second stage during initialization (the second function). Such additional initiation may be a transient increase in temperature, which triggers the secretion of protons in the decomposition of compounds, is introduced to neutralize the emulsion, and which starts the process of curing films of the printed ink. Aqueous coloring composition is preferably used for screen printing. By appropriate selection of the described components, which can be easily carried out by a person skilled in the art, the aqueous paint composition can also be used for flexographic and gravure printing.

The specified catalyst is a chemical compound that lowers the activation threshold of the chemical reaction of a certain type and as a consequence stimulating the specified chemical reaction. By definition, a catalyst is in the same chemical state 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.

The term "chemical functionality" refers to a group of atoms that undergo at least one preferred special type of chemical reaction, for example-HE-SH groups can react with acids or esters in the presence of appropriate catalysts. The specialist in this area is well known for various types of chemical functionality. The correct choice of conditions (e.g. temperature, solvent and the like), the technician can adjust the reaction of chemical compounds containing several what about the chemical functionalities, thus, only one of them will react. For the reaction of the remaining functional groups of the need to change the reaction conditions.

In the context of the present invention, the term "curing (setting)" "curing" refers to such drying, curing or reaction of the printed ink in which the ink is no longer able to be removed from the substrate and to adhere to other substrates above the printed ink. In addition, within certain limits hardening passivates printed ink on the impact of chemical and physical agents of different types.

The term "vaccine" refers to a chemical joining of molecules cross-linking agent to polymer molecules in the emulsion, acrylic and urethaneacrylate copolymer. Modified so the molecules have approximately the same physical properties that they had prior to the grafting reaction.

Smossyvesj properties of acrylic emulsion and urethaneacrylate copolymer, such as those associated with the presence of reaktsionnosposobnykh methylene group, a well-known specialist in this field. Acetoacetate group are widely used for the modification of polymeric bases (for a review of the relevant patents, see International Polymer Science and Technology, vol.26, No. 4, 1999, T79-T87). Siloxane functional group is found in situ in the chain acrylic and urethaneacrylate copolymer in the course of free radical or initiated by the cations of the process of emulsion polymerization in aqueous solution (see EP 0350240 B1 by Rohm & Haas). Acetoacetate or siloxane functional groups react with the pH change as a result of evaporation of amines. It is noteworthy that smossyvesj properties provide education more intensively interconnected polymer network, which increases the resistance of the printed ink. The stability of ink are improved as a result of selection of acrylic emulsion or urethaneacrylate copolymer having zameshivanii properties.

Another advantageous embodiment of the present invention is an aqueous ink composition, the binder system for which select from colloidal acrylic emulsions or urethaneacrylate copolymer emulsion so that the emulsion had a solubility in alkali. Colloidal acrylic emulsion or urethaneacrylate copolymer emulsions are water-based polymers, usually with a low pH value (pH in the range of 2.5 to 6.0). Such solubility ensures the stability of ink, eliminates the risk of the possible separation of the polymer emulsion of the rest of the paint.

Technological properties of the aqueous ink composition can be further improved by choosing acrylic emulsion or urethaneacrylate copolymer having a value of Tgin the temperature range -10° - 50°C. C is Uchenie T gdefines the temperature range within which the state of the emulsion changes from almost solid or highly viscous (glassy state) to a state with low viscosity (liquid state). The value of Tghave an important influence on the ability to process ink composition during printing.

The components of the binder system of the ink composition can be selected from the group comprising acrylic emulsion and urethaneacrylate copolymers with kislotnym number of 10-90 mg KOH/g are Preferred emulsion acrylic or urethaneacrylate copolymer has an acid number of 15-75 mg KOH/g Graft cross-linking of the molecules of the acrylic polymer or urethaneacrylate copolymer is carried out by a carboxyl group. When the value acid number below 10 mg KOH/g grafting of molecules cross-linking agent is rarely exercised, and in that case, when the acid number has a value of 90 mg KOH/g, an acrylic polymer or urethaneacrylate copolymer gain increased sensitivity to the action of solutions of alkali or surface-active substances, resulting in poor water resistance of the printed ink. Another aspect of the present invention relates to a dry matter content of the acrylic emulsion or urethaneacrylate copolymer. The dry matter content in the range of 35-55% in the calculation of the masses of the emulsion allows you to achieve better results (usually acrylic emulsion or urethaneacrylate copolymer emulsion has a solids content in the range of 35-55%, this value represents the content of dry substances in Vodootvodny polymers). The result is increased stability against temperature changes, changes in the composition, the addition of solvents, pH and so on).

Preferred compositions of the aqueous inks of the present invention contain 30-70% emulsion sumassheshego acrylic or urethaneacrylate copolymer, based on the total weight of the composition. Selected mass amount of the emulsion provides a sufficient amount of binder to achieve the necessary resistance to chemical agents and physical treatments. The selected amount of the emulsion provides sufficient wetting of the pigment and improves water transfer ink from the printing plate to the substrate (with flexographic printing forms on paper or with the plate cylinder to the paper). In the preferred compositions of printing inks mass amount of acrylic emulsion or urethaneacrylate copolymer is 35-60%, more preferred compositions of 40-55% by weight. calculated on the total weight of the composition.

An important aspect of the present invention is a crosslinking agent chosen from the group of substituted alkoxysilanes (R1)y(R2O)zSi. R1and R2represent different organic substituents, and the bottom is indexy y and z must satisfy the equation y+z=4. The preferred crosslinking agent is chosen from the group monosubstituted trialconsistent (in which y=1 and z=3). The substituents R1and R2contain functional groups that differ from each other. This difference allows you to adjust the process connection/reaction of the various components in the prepared formulation of paints and/or in the substrate in various stages of applying paint. The preferred crosslinking agent is chosen from the group monosubstituted of triethoxysilane. The specified crosslinking agent contains epoxy functional group (first functional group), and more preferably, when a crosslinking agent is chosen from the group comprising epoxy-cycloaliphatic triethoxysilane and glycidylmethacrylate. Epoxy functionality, which is the first functionality is intended to react with the functional groups of the binder system, in particular with the free carboxyl groups. Anhydrides of acids may react with epoxides in the presence of a catalyst.

These epoxypropyl after the induction period react with functional groups of acrylic or urethaneacrylate copolymer emulsion. A second functionality (consisting of taksigrup) cross-linking agent is intended for reaction during hardening (setting) printed the or ink into. The reaction is initiated by the change of pH in a colorful film (hydrolysis). The change in pH occurs in the decomposition of chemical compounds that are part of the paint ingredients, and it is necessary to neutralize the functional groups of the binder components. During the specified decomposition evaporation of ammonia or volatile amines, members of the neutralizing agent.

Another aspect of the present invention is that the aqueous ink composition contains a crosslinking agent in the amount of 0.25 to 3% by weight of the total composition. Outside these limits the amount of cross-linking agent is unable to create a sufficiently linked polymer network, or in excess of the specified number of action linking agent leads to the formation of too short polymer chains, with a high degree of crosslinking, which impairs the mechanical and chemical stability of the polymer and, consequently, the printed ink. The preferred composition contains a crosslinking agent in the amount of 0.5-2%, more preferably 1-2%, based on the total weight of ink composition.

In accordance with another aspect of the present invention in the composition of the ink introducing the catalyst. The catalyst is chosen from the group of imidazoles, and the preferred compound of this group is 2-ethyl-4-methylimidazo the L. Because the catalyst accelerates the reaction of functional groups of the binder component with the specified siloxane compounds, in the presence of catalyst can be reduced by the amount of cross-linking agent. The content of the catalyst in the ink composition is from 0.05 to 0.6%, based on the weight of the paint composition. The amount of catalyst is preferably selected from a range of 0.1 to 0.4% and more preferably in the interval of 0.2-0.4% wt. calculated on the total mass of the ink formulation.

It is established that the stability and shelf life of the paint can be improved by setting the pH of the aqueous ink composition in the range of 7.0-8.5 in. The preferred composition of the printing ink has a pH value in the range of 7.5 to 8.3, and even more preferred composition has a pH value in the range of 7.5 to 8.0. Correction of pH is important for the stability of alkoxy fragments cross-linking agent in the presence of water, since it is known that these chemical functional groups do not have the stability against hydrolysis at elevated pH values. Too high pH values reduce the shelf life of the composition of the water-based ink.

Another aspect of the present invention relates to the selection of the appropriate number of pigments in the ink composition. The amount of pigment in the calculation on the total weight of the paint composition is from 10 to 25 wt.%, PR is doctitle 12-20 wt.%. and even more preferably 15-18% wt.

In accordance with a particular embodiment of the composition of the aqueous printing ink pigment selected from the group valuable pigments having such physical properties as a selective spectral absorption, luminescence, magnetism, electromagnetic resonance, optical effects, etc. In the context of the present invention is particularly interesting pigments consisting of scales from the first and second flat parallel surfaces. The preferred amount of the said pigment flakes, meaning in the context of the present invention the ratio of their length to the height value is larger than two, and more preferably more than five.

Another part of the present invention relates to a method for production of the composition of water-based paints. This method includes at least four stages:

- in the first stage are acrylic emulsion or urethaneacrylate copolymer,

on the second, optional phase in the specified polymer emulsion type catalyst, pigment and other optional additives

next, the third stage add a crosslinking agent capable of reacting with the acrylic emulsion or urethaneacrylate copolymer,

- in the fourth stage conduct thorough mixing of the emulsion acrylic or urethaneacrylate copolymer, not batteling catalyst, optional pigments and other optional additives with cross-linking agent added in the third stage, and the exercise of their chemical interaction with the formation of covalent bonds between the molecules of the crosslinking agent and the molecules of the acrylic emulsion or urethaneacrylate copolymer.

The described method provides the composition of the water-based ink, suitable for screen printing and possessing good stability during storage, thus demonstrating the properties (such as viscosity)required for use in screen printing.

Production of paint in accordance with the proposed method (proposed by the sequence of stages) guarantees excellent print properties and stability of the printed and cured ink.

Another aspect of the present invention relates to the application of water-based ink composition for screen printing, printing with elastic forms (flexography or gravure printing. The specified paint composition includes acrylic emulsion or urethaneacrylate copolymer and a crosslinking agent, in which the crosslinking agent reacts with the components of the emulsion, acrylic or urethaneacrylate copolymer before printing, and the specified emulsion acrylic or urethaneacrylate copolymer chosen from the group of emulsions having the properties clossiana. The composition of the printing ink should the AK to condition for printing, to fully carried out the reaction of grafting, cross-linking agent to the molecules of the acrylic emulsion or urethaneacrylate copolymer. This grafting reaction is usually carried out for 2-4 days.

Thus, you can be sure that the hydrolysis of the second functional cross-linking agent (corresponding to the curing of the printed ink) will take place with the participation of the grafted molecules emulsion and as a result will be achieved the intended excellent resistance paint to chemical and physical agents.

Another aspect of the present invention relates to a valuable document with the font, which is obtained as a result of printing using water-based ink composition of the present invention, designed for screen printing, the print with elastic forms and gravure printing. Printed and cured ink satisfies the special requirements of resistance to chemical and physical agents.

The following sections give a more detailed explanation of the present invention using non-restrictive examples of the compositions shown only for illustrative purposes.

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

- Neocryl XK-11 NeoResins/Avecia

-Neocryl XK-14 NeoResins/Avecia

- Neocryl BT9 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 derived polyaniline

- Zonyl UR Dupont Fluoride surfactant

Water-based ink for stencil printing is obtained using the following cetoscarus optically changeable pigments and fluorescent/phosphorescent pigments:

- bright colors: Iriodin (Merck), Paliosecure, Paliogene, Paliotol, Paliochrome (BASF), Mearlin Dynacolor, ICP and Mearl (Engelhard), Flonac (Eckart).

- Paint with color distortion (LCD based): LCP, SLM, Helicone HC (Wacker).

- Paint with color distortion (without LCD base):

Variochrom (BASF), Colorcrypt (Marck), Chromaflair (Flex).

- Optically variable ink (OVI™): OVP™ (Flex).

The test chemical and physical properties was performed by following the standard method.

Acrylic and polyurethane emulsion in all trials was used with semi-automatic gruntovalnoy machine on afluorescent paper for making money. The true fluorescence was determined at length UV irradiation at 254 and 366 nm.

Water-based ink for stencil printing, containing cetoscarus or optically variable pigments, used on valuable paper for making money using p is lautomatically gruntovalnoy machine (handheld device for coating No. 3, the wet film thickness of 24 μm). The paint is applied, dried for 30 seconds at 80°and nail examined the adhesion of paint.

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 the wet state (=WR) and dry (=DR) and were tested by washing (in accordance with the rules INTERPOL established 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. To select the best emulsion water paint for screen printing is usually subjected to two tests for washing and test for resistance to abrasion in wet condition. Typically, such testing is carried out after 7, 15 and/or 30 days in order to capture long-term effects of the stitching.

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. The treated paper is smooth and the enemy is up 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: test abrasion in dry condition was performed 100 times using weight 610 g, and the 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 ispytannaya, 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. Good 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%

(a) Compounds water-based ink for rotary screen printing:

Example 1

The paint samples were prepared from the following structures:

For all formulations was selected content of the dry resin 18-20%, and the concentration of acrylic/polyurethane emulsions were chosen in accordance with the content of solid substances (column 3). Konz is ntrace pigment (Iriodin fine Gold) was 16.5-18%, in addition to the system was added 3% wax (Jonwax 22, S.C.Johnson Polymer), 6% cholesterolic solvents or co-solvents (diethylene glycol, methyl ether of dipropyleneglycol, Texanol) and 2% additive (Byk 24, BYK-Chemie). The final viscosity of the composition was controlled by means of thickeners (Pheolat 278, Rheox) to get the value of the viscosity of 800-1000 MPa·C, after which the formulation was supplemented with water to 100%.

ProductProviderSolids, %Acid number/ mg KOH/gTg/[°C]MFT/[°C]pH
Neocryl XK-11NeoResins431925338,1
Neocryl XK-14(Avecia)37,5550338,6
Armorez CR2900Westvaco4118155,0

Samples were prepared using the above composition, and the sample 1 contained Neocryl XK-11, sample 2, Neocryl XK-14 and sample 3 - Armorez CR2900 as acrylic/polyurethane emulsion, respectively.

Prepared bright colors, took notes and perform the test.

The test results in the washing Rast is the PR under stirring:

SampleProductLSS* Sustainability/5 daysThe creasing in the dry state/5 daysThe creasing wet/5 daysLSS Sustainability/5 days
1Neocryl
5,5-5,9665,1-5,9
HC-11
2Neocryl
5,1566a 4.9
XK-14
3Armorez
5665,33
CR2900
*LSS: washing solution + re is eshiwani

4 sample:

The paint composition in the sample 1 was changed so that added 2% CoatOSiL® Y-11988, and the pH of the ink was set in the range of 8.0 to 8.3 and, if necessary, using the AMR-95.

The paint was kept at room temperature for 3 days before printing to ensure reaction between the crosslinking agent and the emulsion. The paint was printed, dried and tested after 7 and 30 days.

The results of the test sample145
The test of washing after 7 daysS.1+0,5%

CX-100
S.1+2%Y-11988
LSS*1,55,55,6-5,85
LWM*3,75,34,7-5,5
The test of washing after 30 days8.1+0,5%

CX-100
S.1+2%Y-11988
LWM*5of 5.45,4-5,6
*LWM: machine washable; LSS: washing solution + mixing

The tests have demonstrated excellent stability of formulations of ink, which can be judged by the results of measurement of viscosity (Brookfield Viscometer Model DV-I+) samples 1 and 5 at 25 and 40°C.

Hung is for the viscosity of the ink composition from the time of storage:

DaysArr. 1:25°Arr. 1: 40°Arr. 5: 25°Arr. 5:40°
0795830
3890920735735
6880690
9855920650765
16845945638728
23840963648713
308631105660705
668181722653655
92808640728

Example 2

The influence of the used amount of crosslinking agent in the washing solution and the resistance to washing machine, respectively.

Samples 6, 7 and 8:

Used the paint composition corresponding to sample 5, except that instead of CoatOSil® Y11988 used a more sustainable CoatOSil® 1770. Sample 6 contained 0.15% of CoatOSil® 1770, sample 7 - 0,25% CoatOSil#x000AE; 1770, and the sample 8 contained 0.5% of CoatOSil® 1770. In each case, the amount of crosslinking agent was 20% based on the weight of dry resin.

The test results of the composition of the printing inks with different content of crosslinking agent:

Sample 6Sample 7Sample 8
0,15%0,25%0,50%
MonthsLWM*LSS*LWM*LSS*LWM*LSS*
04,62,154,852,93,04,85
14,64,54,255,154,755,85
2the 5.654,655,62,355,04,5
34,64,04,353,852,6a 4.9
*LWM: washing in a washing machine; LSS: washing solution + mixing

Example 3

The influence of the catalyst on the washing solution and stability to the machine stirk the respectively.

Samples 9, 10 and 11:

In the printing ink compositions of the samples 6, 7 and 8 were added to the catalyst EMI-24 in a mass ratio of 0.2 relative to the amount of cross-linking agent.

The test results of the composition of the paint if you change the quantity of catalyst:

Sample 9Sample 10Sample 11
Catalyst0,03%0,05%0,10%
MonthsLWM*LSS*LWM*LSS*LWM*LSS*
04,335,584,55,58a 4.835,58
14,924,254,754,54,085,5
2of 5.75a 4.835,67a 4.835,165,67
34,584,54,335,00,83of 5.75
*LWM: washing in a washing machine; LSS: washing solution + mixing

Example 4

One-component water-based ink compositions, the content of Asia optically variable pigments or pigments with optical effect.

Optically variable pigments or pigments with optical effect can be produced in different ways and well-known specialists in this field of technology. Depending on their chemical nature of optically variable pigments may have a different resistance to the conditions existing in the formulation of printing inks. In some cases they should be Passepartout using appropriate methods and with the use of chemicals.

Samples 12 and 14 contain passivated optically variable pigments. Samples 13 and 15 contain the same optically variable pigments, but not in the passivated state. Samples of paint were obtained by the following method:

Sample 12:

1. In situ passivation of the pigment in water:

Methyl ether of propylene glycol6,0
Zonyl UR0,5
Water22,0
OVP green/blue15,0
AMR-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 min is so

2. Preparation of paint:

Neocryl XK-1148,0
Zonwax 223,0
Byk 024 (BYK-Chemie)1,9
Byk 025 (BYK-Chemie)0,1
Aerosil 200 (Degussa)1,0
CoatOSil 17701,0
Silwet L-7608 (Witco)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 Siwet L-7608.

2. Adjusting the viscosity:

Water1,7
Rheolat 278055

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 13). In the same way were prepared paint containing pigment Chromaflair™ (color change from purple to yellow), in the presence or absence of Zonyl UR (Example 14 and 15).

Sample 12Sample 13Sample 14Sample 15
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

(b) Compounds water-based ink for screen printing (flat printing machine:

Example 5

General method of preparation of paints:

Deionized waterx
Co-solvents6,0
AMR-95
Acrylic emulsion (dry matter: 19%)42-57
Byk 0242,0
Jonwax 223,0
Iriodin fine-grained, Golden18,0
Thickenerz
Only97,00

With stirring to water and co-solvents were simultaneously added AMR-95 and acrylic emulsion (alkali-soluble). The amount of water and ammonia was calculated in accordance with the value of the acid number and the solids content of each emulsion. The pH value of the ink was set in the range of 7.5 to 7.7 using AMR-95. The viscosity of the ink was adjusted in the range of 800-1000 MPa·using thickener Rheolat 278.

Physical properties of acrylic emulsions:

EmulsionThe solids content of/[%]Tg/[°C]Acid number (mg KOH/g)
Neocryl BT-940172
Neocryl BT-20402960

The sample contains 16 emulsion Neocryl BT-9, sample 17 - emulsion Neocryl BT-20, respectively.

Each recipe paint was added 2% CoatOSil® 1770 (based on the total weight of the composition) and min after the high storage for 3 days at ambient temperature paint used on valuable paper for making money using semi-automated gruntovalnoy machine (handheld device for coating No. 3, the wet film thickness of 24 μm). The paint is applied, dried for 60 seconds at 80°and the adhesion was tested by scraping with a fingernail.

The test results of the compositions of the ink with cross-linking agent

Tg/[°]Washing machine/7 daysWashing machine/ 30 days
Sample 169the 5.65the 5.65
Sample 1729the 3.85,6

Example 6

The effect of added quantities of cross-linking agent.

The formulation of the paint according to Example 5 was prepared using Neocryl BT-20 as an acrylic emulsion. To the resulting paint was added CoatOSil® 1770 in the amount of 1% (sample 18) and 2% (sample 19) based on the dry weight of solid resin.

The paint was left for three days at room temperature and then was applied (printed) onto the paper for the manufacture of banknotes. Through 7,15, 30 and 60 days printed samples were tested by washing in a washing machine and washing processing solution.

The results of tests with different amounts of cross-linking agent

Sample 18 Sample 19
DaysLWM*LSS*LWM*LSS*
70,300,003,200,20
151,321,025,425,17
301,800,375,425,67
605,582,75of 5.835,67
*LWM: washing in a washing machine; LSS: washing solution + mixing

1. The composition of the water-based ink for stencil printing, containing (a) an acrylic emulsion or urethaneacrylate copolymer in the amount of 30-70%, preferably 35-60% and more preferably 40-55 wt.% Samodiva emulsion acrylic or urethaneacrylate copolymer calculated on the total weight of the composition; (b) a crosslinking agent in the amount of 0.25 to 3%, preferably 0.5 to 2% and even more preferably 1-2 wt.% the specified crosslinking agent, calculated on the total weight of the composition; (c) an optional catalyst; (d) an optional pigment; and (e) an optional additive, characterized in that the crosslinking agent contains at least two different functionalities in a single molecule, and the first of these functions is chosen in such a way as to form Kowal is NTUU communication with said polymer to print, and the second of these functions is chosen in such a way as to carry out the crosslinking of the specified polymer to curing of the printed ink, and acrylic emulsion or urethaneacrylate copolymer selected from the group having the properties clossiana, and the composition has a pH from 7.0 to 8.5, preferably from 7.5 to 8.3 and more preferably from 7.5 to 8.0.

2. The composition according to claim 1, characterized in that the acrylic emulsion or urethaneacrylate copolymer soluble in an alkaline environment.

3. The composition according to any one of claim 1 or 2, characterized in that the acrylic or urethaneacrylate copolymer has a value of Tgin the temperature range -10 to +50°C.

4. The composition according to any one of claims 1 and 2, characterized in that the acrylic emulsion or urethaneacrylate copolymer has an acid number in the range of 10-90 mg KOH/g, preferably 15-75 mg KOH/g

5. The composition according to any one of claims 1 and 2, characterized in that the acrylic emulsion or urethaneacrylate copolymer contains 35-55 wt.% solids based on the weight of the emulsion.

6. The composition according to claim 1, characterized in that the crosslinking agent is chosen from the group of substituted alkoxysilanes (R1)y(R2O)zSi, where R1, R2represent different substituents, y+z=4, preferably from the group monosubstituted trialconsistent (y=1, z=3).

7. The composition according to claim 1, distinguished by the different topics the specified crosslinking agent selected from the group monosubstituted of triethoxysilane, preferably from the group comprising epoxycyclohexane triethoxysilane and glycidylmethacrylate.

8. The composition according to claim 1, characterized in that the catalyst is chosen from the group of imidazoles.

9. The composition according to claim 1, characterized in that it contains 0.05%and-0.6%, preferably 0.1 to 0.4%, and even more preferably 0.2 to 0.4 wt.% catalyst based on the total weight of the composition.

10. The composition according to any one of claims 1 and 2, characterized in that it contains 10-25% of pigments, preferably 12-20% and even more preferably 15-18%, based on the total weight of the composition.

11. The composition according to any one of claims 1 and 2, characterized in that the pigment is selected from the group consisting of fluorescent pigments, magnetic pigments, pigments, optical effect and optically changeable pigments, in particular of the layered pigment having first and second flat parallel surfaces and dimensional relationship of more than two, preferably more than five.

12. The method of producing water-based ink composition for screen printing, as claimed in claims 1 and 11, characterized in that it comprises the following stages: (a) preparation of emulsion acrylic or urethaneacrylate copolymer; (b) the optional preparation of the catalyst, an optional pigment, and optional additives; (c) preparation sshi is non-agent, capable of forming covalent bonds in the initial conditions of the polymer prepared in (a), and joining the resulting polymer second conditions;

(d) thorough mixing of the components prepared in paragraphs (a), (b)and (C), and connectivity of the polymer obtained in (a) with a crosslinking agent obtained in (C) in said first conditions; (e) adjusting the pH of the composition to the range of 7.0 to 8.5.

13. The use of the composition of water-based paints, including acrylic emulsion or urethaneacrylate copolymer as from 30 to 70 wt.%, preferably from 35 to 60 wt.% and more preferably from 40 to 55 wt.% Samodiva emulsion acrylic or urethaneacrylate copolymer calculated on the total weight of the composition and a crosslinking agent in an amount of from 0.25 to 3%, preferably from 0.5 to 2%, and more preferably from 1 to 2 wt.% the specified crosslinking agent, calculated on the total weight of the composition as an ink for screen printing, and a crosslinking agent covalently bonded with acrylic or urethaneacrylate copolymer, and acrylic emulsion or urethaneacrylate copolymer selected from the group of substances with zameshivanii properties, and the composition has a pH from 7.0 to 8.5, preferably from 7.5 to 8.3 and more preferably from 7.0 to 8.0.

14. Valuable document with signs, nab is dataname using water-based ink composition for screen, flexographic or gravure printing, as claimed in claims 1 to 11.



 

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