Adhesion activating compound

FIELD: chemistry.

SUBSTANCE: described is an activator of adhesion of ink to a substrate, containing a product of reaction of (a) a polymer solution or synthetic resin, (b) sulphonic acid or derivative thereof and (c) a metal compound selected from a group consisting of a metal halide, metal alkoxide, metal halide-alkoxide or a condensed metal alkoxide, where the metal is titanium or zirconium. The amount of sulphonic acid or sulphonic acid salt (b) and metal compound (c) corresponds to molar ratio of SO3X, where X is a H atom or a base residue, to Ti and Zr atoms ranging from 0.25:1 to 2:1. The invention also describes printing ink containing said adhesion activator.

EFFECT: reduced yellowing and smell of ink compared to ink which contains titanium acetyl acetonate as an adhesion activator while preserving effectiveness of the adhesion activator.

22 cl, 4 tbl, 15 ex

 

The present invention relates to the adhesion promoters, in particular, to improve the adhesion of printing inks to the substrate on which the applied ink, and ink formulations for printing containing the adhesion promoters.

Compounds that activate adhesion, are used in industrial ink formulations to enhance the adhesion between the ink and substrate, which is a printing ink. The lack of adhesion leads to difficulties in the printing process or unintentional deletion of printing. Printing on plastic food packaging is widely distributed, and is particularly important in such applications to printed ink remained on the packaging and that part of the ink compositions do not contaminate the product.

The adhesion promoters on the basis of titanium compounds are known and for many years was used in industry. Although simple compounds of titanium, such as titanium acetylacetonates, provide good adhesion between the ink and substrate, they tended to give the ink undesirable yellow color and smell. In the document GB-A-2161811 described adhesion promoters, which represents organotitanate comprising the reaction product of complex orthoevra titanium and at least monoalkylated (for example, a mixture of monoalkylated and dialkylphosphate), in which the alkyl group sumergido 6 carbon atoms and in which the total molar ratio P:Ti in the product is less than 2. Such compositions provide effective activation of adhesion with much less yellowing and odor than the above titanium compounds, and have commercial success. In each of the documents WO 2005/049662 and WO 2005/097919 described alternative activators of adhesion produced by the joint interaction of titanium compounds, phosphorus compounds and resins.

Applicants currently manufactured adhesion promoters for ink, which has superior properties compared to compositions of the prior art, and which permits to avoid the inclusion in the composition of the ink organophosphate connections.

In accordance with the invention, applicants are adhesion promoters suitable for use in ink formulations for printing to activate the adhesion of printing ink to a substrate, comprising the product of a collaborative interaction:

(a) a solution of a polymer or synthetic resin,

(b) sulfonic acid or a derivative of sulfonic acid and

(C) compounds of a metal selected from one or more of the group consisting of metal halide, metal alkoxide, halide-metal alkoxide or condensed alkoxide of metal, where the metal is selected from titanium or zirconium.

In accordance with the second aspect of the invention, the applicants are printed ink, including:

i) a polymer with anywayse substance,

ii) a solvent for the polymeric binder, and

iii) adhesion promoters comprising the product of a collaborative interaction

(a) a solution of a polymer or synthetic resin,

(b) sulfonic acid or a derivative of sulfonic acid and

(C) compounds of a metal selected from one or more of the group consisting of metal halide, metal alkoxide, halide-metal alkoxide or condensed alkoxide of metal, where the metal is selected from titanium or zirconium.

In accordance with a third aspect of the invention, the applicants represent a method of manufacturing a compound that activates adhesion, which includes stages:

(a) mixing a solution of a polymer or synthetic resin with sulfonic acid or a derivative of sulphonic acid and then

(b) mixing the mixture formed in stage (a)with a compound of the metal selected from one or more of the group consisting of metal halide, metal alkoxide, halide-metal alkoxide or condensed alkoxide of metal, where the metal is selected from titanium or zirconium.

In the present description the terms "adhesion promoters" and "connection, activating adhesion" have essentially the same meaning and may be used interchangeably.

The polymer or synthetic resin preferably represents a hydroxyl-containing the maul, suitable for use in printing ink. Fit hydroxycobalamin resins preferably have a hydroxyl number from about 100 to about 500 mg KOH/g, in particular from about 200 to about 400 mg KOH/g (tested in accordance with DIN 53240). Examples of suitable synthetic resins include ketoaldehyde resin, in particular reconformation resins, such as hydrogenated resin condensation of acetophenone and formaldehyde resin condensation of cyclohexanone-formaldehyde and modified urethane ketoaldehyde resin. Such resins are available from the company Degussa AG, for example, in the form of synthetic resins 1201, CA and SK.

The polymer or synthetic resin dissolved in a suitable solvent, such as alcohol or ester, such as propyl, ethyl acetate, ethanol or mixtures thereof. This solution preferably contains from about 10% to 70% resin by weight, in particular from 20% to 60% resin by weight. The amount of resin depends on its solubility in the solvent and mobility of end connections, activating adhesion.

Connection sulfonic acid selected from any readily available organic sulfonic acids, including alkyl - and arylsulfonic acid. Examples of suitable sulfonic acids include methanesulfonate acid and dodecylbenzenesulfonic acid. That is also suitable derivatives of these sulfonic acids, for example, alkali metal salts such as sodium salt and Quaternary ammonium salt or a derivative formed by reaction of the sulfonic acid with an amine to education sulfonamida. Suitable amines include, without limitation, the bonds alkylamines, in particular tertiary amines, and alkanolamines, of which the preferred ethanolamines. Derived sulfonic acid can be formed either before or after mixing the sulfonic acid with a polymer/resin, metal connection, mixture or reaction product of any of them. For example, the joint product of the interaction of polymer, metal joining and sulfonic acids can interact with the basis for the formation of a derivative of sulfonic acid to increase the pH of the product. In a preferred embodiment, at least some amount of sulfonic acid or sulfonic acid residues in the reaction product with a compound of the metal and resin interacts with triethanolamine. Unless the context indicates otherwise, the term "sulfonic acid"used in this description, is intended to denote a sulfonic acid or a derivative of sulfonic acid. Sulfonic acid may be mixed or dissolved in the solvent or other miscible diluent prior to mixing with other reagents. Suitable Rast is oriali or diluents include alkalemia alcohols and complex alkalemia esters, such as ethanol, propanol, butanol, propyl and ethyl acetate.

The compound of the metal selected from one or more of the group consisting of metal halide, metal alkoxide, halide-metal alkoxide or condensed alkoxide of metal, it may include a mixture of these compounds. Preferably the metal is titanium, and the preferred titanium compounds include titanium alkoxides having the General formula Ti(OR)4in which R represents an alkyl group, preferably having 1 to 8 carbon atoms. Each group R may be the same or different from other groups of R. Especially suitable alkoxides include tetraisopropoxide (tetraisopalmitate), Tetra-n-butoxysilane (Tetra-n-butylsilane) and tetraethoxysilane (tetraethylthiuram). You can also use the alkoxides of zirconium, such as n-propoxide Zirconia.

Condensed alkoxides are usually obtained by careful hydrolysis of the alkoxides of titanium, and they can be represented by the formula, R1O[Ti(OR1)2O]nR1in which R1represents an alkyl group. Preferably n is less than 20 and more preferably less 10. Preferably R1contains 1-6 carbon atoms, and useful condensed alkoxides include compounds known as polybutylene and polyisopropylene.

The number is the proportion of the resin solution, the titanium compounds and sulfonic acid used for the manufacture of adhesion promoters, to some extent depends on the nature of the selected compounds. Preferably, the amount of coupling metal and resin provided the molar ratio of OH:Ti or Zr in the range from 0.25:1 to 4:1, more preferably 0.5 to 2:1, where the content IT represents a lot of IT is derived from the resin component, calculated from the hydroxyl value of the resin, expressed as mg KOH/g

Used the number of sulfonic acid and compounds of metal preferably chosen to ensure a molar ratio of the groups SO3X to the atoms of Ti or Zr in the range from 0.25 to 2:1, it is often in the region of 0.5 to 1.75:1. SO3X represents a functional group sulfonic acid or a derivative of sulfonic acid, where X represents the atom H or a residue of a base, such as metal, Quaternary ammonium or aminocell.

The adhesion promoters can be produced by mixing the reactants in any order. It is preferable to mix the first solution of the resin with sulfonic acid, and then mixing the resulting mixture with a compound of the metal. Preferably, the compound of the metal was added to the mixture solution of the resin and the sulfonic acid. Possible, but less preferably, the addition of a mixture of resin solution and Sul the background of the acid to the compound of the metal. The mixing of the solution of resin with sulfonic acid may be accompanied by a visible color change and/or heat, indicating a reaction between the components of the mixture. The reaction mixture compounds resin/sulfonic acid with a compound of the metal is usually exothermic and may also lead to thickening of the mixture. Ectothermy can be adjusted by cooling the reaction mixture and the slow and careful addition of metal joining. When there is thickening, add more metal link may cause to reduce the viscosity of the mixture.

Alternative adhesion promoters may be manufactured by first mixing together the compounds of the metal with the resin solution and then adding the sulfonic acid to the resulting mixture. As another alternative, sulfonic acid can interact with metal connection, and the resulting mixture is then added to the resin solution. When the components of the adhesion promoters mixed together, can produce some by-products. Usually, when the metal alkoxide reacts with the resin or with a sulfonic acid, a molecule of the alcohol is displaced from the metal. If required, the alcohol can be removed from the reaction mixture by distillation or other suitable means. Typically, the alcohol remains in the mixture of adhesion promoters, and therefore VC is positive to choose the appropriate metal compounds to ensure that to by-products did not give undesirable properties of the adhesion promoters or ink compositions, which assumes the use of adhesion promoters.

Product as adhesion promoters may additionally include a solvent or mixed solvent. The reaction product of a compound of metal, resin and the sulfonic acid can be mixed with a suitable solvent or diluent such as an alcohol, in particular alkilany alcohol, and complex alkalemia esters, such as ethanol, propanol, butanol, propyl and ethyl acetate. Particularly suitable solvents or diluents include ethanol or propanol, especially in the form of denaturirovannykh alcohols, i.e. a mixture of alcohols and, optionally, other compounds.

The adhesion promoters according to the present invention can be used in various coating compositions, for example, metals, etc. but it is in particular used in flexographic and gravure ink containing the polymer-binding compound that can undergo cross-linking and which is dissolved in an appropriate organic solvent. The printing inks according to the invention usually also belong to the specified type. Typical binders used in such inks are binding substances on the basis of nitrocellulose or modifitsirovannoi cellulose type of ester, for example acetotrophic cellulose. Often, these polymeric binders are used in a mixed form, polyamides, polyurethanes or other resins. The ink also typically contain one or more pigments and/or one or more dyes. Typical pigments that can be used are colored inorganic pigments, white inorganic pigments and colored organic pigments. Organic dyes can be used to make the ink of the corresponding color, and they are often used in combination with giving the opacity of the white inorganic pigment such as titanium dioxide. The printing ink of the present invention need not include a pigment and/or dye. In the absence of pigment or dye ink composition is often referred to as varnish. Varnishes can be obtained for application in non-pigmented condition on the substrate or they can be obtained to obtain later color ink or coating by adding a pigment or dye, which can be dispersed in the form of a concentrate or master batch, a number similar to the ink composition. The ink of the present invention may contain other additives, such as agents that promote the slip, and plasticizers.

The ink of the present invention is usual contain adhesion promoters in an amount up to 10 wt.% the total ink weight, and preferably in an amount of from 1 to 6 wt.% the ink. Applicants have found that the adhesion promoters of the present invention is particularly effective and that they can therefore be used at lower concentrations than known activators of adhesion. Therefore, in some applications, the adhesion promoters are added to the ink in the amount of 1-3% of the total mass of the ink. When the adhesion promoters used in the composition of the main party, its concentration may be much higher (e.g. up to 20%), but it will usually be mixed with other components of the ink before printing.

The ink of the present invention, in particular, are used when printing on substrates formed from polymeric materials, especially films, such as films used in packaging, particularly food packaging. Examples of such substrates include complex polyester, polypropylene, polyethylene or foil or the sheets of polypropylene/polyethylene subjected to co-extrusion, and plastic materials, coated grades, but this list is not intended to be limiting.

Hereinafter the invention will be described in the following examples.

Test adhesion of ink

Want to test the connection of the adhesion promoters were added to test the ink on the basis of TiO2(described below) and mixed. The application of ink has been corona treated and discharges polypropylene film using K-bar number 2. The film was dried, making four passes over the silicon bar at 60°C, and then held the test of adhesion to the tape using opaque red tape Scapa width of 50 mm Cellulose Splice Red Tape Type 1112”. The results were determined by the percentage of ink remaining in the test after removing the masking tape. Two subject comparison of ink were applied side by side on the same film substrate and a single strip of masking tape was placed on top of both samples of ink together to ensure identical test conditions. In this series of tests, one sample of ink contained adhesion promoters, shown in the table, while the other ink not containing adhesion promoters, served as control. You can then directly compare the amount of ink remaining on the substrate, expressed as a percentage of the ink before the test.

Test ink

Standard test inks were made using the following ingredients are represented by parts by weight:

IngredientSolution 1Solution 2
Denatured alcohol62,6to 75.2
The ethyl acetate 93,9112,7
Nitrocellulose DLX 3/5*57,468,9
Sylvaprint 8250**-10,0
Resin SK***-25,1
Pigment TiO2365,4-
Solution 2243,2
Polyurethane resin****177,5-
Only1000,0
* from Nobel Enterprises
** derived resins from Arizona Chemical
**** from the company Degussa AG
**** UnithaneTMfrom Cray Valley Ltd

To prepare the solutions 1 and 2. Add TiO2to a solution of 1 and dispersing. Add a solution of 2 in the base of the mill and mix. Add polyurethane and mix. Filtered and brought to the printing viscosity by the mixture of ethyl acetate/ethanol in a ratio of 50:50 (approximately 25 cups Zahn No. 2). The adhesion promoters added as the final component cher the sludge and mix. The used amount of the adhesion promoters are shown in the table. The ink is printed and tested for adhesion immediately after mixing with adhesion promoters. Then some samples of ink give the opportunity to be exposed to conditions of aging in the period up to two weeks before printing and testing. The results obtained with these samples indicate the shelf life of adhesion promoters during storage.

Example 1 (comparative)

50% (wt./wt.) solution “Synthetic Resin SK”TMavailable from Degussa AG and having a hydroxyl number of about 325 (in accordance with reference specification sheet from the manufacturer), produced in n-propyl. Further, this solution will be referred to as solution SK50. To 87,7 g of the solution SK50 added to 50.7 g (0.25 mol) of phosphate amyl acid (approximately 1:1 complex of mono - and diesters) when mixing. The color of the solution changed from very pale yellow to orange. When the phosphate was added to the resin solution and the solution was mixed for 5 minutes to orange solution slowly while mixing was added 71 g (0.25 mol) of Tetra(isopropyl)titanate (VERTECTMTIPT, available from Johnson Matthey Catalysts). The mixture was thickened after adding TIPT, but became thinner as you continue adding. When you are finished adding the product was mixed for another 5 minutes and the eat was transferred into a sealed container for the sample. The product sample was then added to the test ink composition as above, and tested for the assessment of activating the adhesion effect, as described above in the test ink. The results are shown in table 1.

Example 2

116,5 g of 70% solution dodecylbenzenesulfonic acid in isopropanol was added to 87,7 g of the solution SK50 under stirring. The color of the solution changed from very pale yellow to orange. The solution was allowed to mix for 5 minutes, and then to orange solution slowly while mixing was added 71 g (0.25 mol) of Tetra(isopropyl)titanate (VERTECTMTIPT, from Johnson Matthey Catalysts). The molar ratio of sulfonic acid to titanium was 1:1. The molar ratio of hydroxyl groups on the resin to titanium atoms was approximately 1:1. When the addition was completed, the product was mixed for another 5 minutes and then transferred into a sealed container for samples. Then a sample of the product was added to subject the ink composition as described above and then tested for the assessment of activating the adhesion effect, as described above in the test ink. The results are shown in table 1.

Example 3

Repeating the procedure of preparation described in example 2, except that used only a 58.3 g of the solution dodecylbenzenesulfonic acid to obtain a molar ratio of AlfaNova acid to titanium of 0.5:1.

Example 4

71 g (0.25 mol) of Tetra(isopropyl)titanate was added to 87,7 g of the solution SK50 under stirring. The solution was allowed to mix for 5 minutes, and then to the resulting solution slowly while mixing was added 116,5 g of 70% solution dodecylbenzenesulfonic acid in isopropanol. The molar ratio of sulfonic acid to titanium, to the hydroxyl groups on the resin was 1:1:1. When the mixture was complete, the product was transferred into a sealed container for samples. Then a sample of the product was added to subject the ink composition described above and then tested for the assessment of activating the adhesion effect, as described above in the test ink. The results are shown in table 1.

Example 5 (comparative)

Inks were made using the same ink composition, but using as adhesion promoters with the sale of the product, VERTECTMR, which represents the adhesion promoters containing acetylacetone.

Table 1
The adhesion promotersThe adhesion promoters, wt.%
1%2%3%
Fresh1 week2 weeks
No (comparative)2020202020
Example 1 (comparative)-82989898
Example 295100100100100
Example 38598100100100
Example 497100100100100
Example 5 (comparative)--989898

Example 6

388,5 g of a 50% solution dodecylbenzenesulfonic acid from the propanol was slowly added to 195 g of the solution SK50 under stirring. To the solution slowly while mixing was added 246 g of a 75% solution of Tetra(n-propyl)of lead zirconate in n-propanol (of 0.56 mol Zr). When you are finished adding the product was mixed for another 5 minutes and then transferred into a sealed container for samples. The molar ratio of OH:SO3H:Zr in the product was 1,0:1,1:1,0. Then a sample of the product was added to subject the ink composition as described above and then tested for the assessment of activating the adhesion effect, as described above in the test ink. The results are shown in table 2.

Example 7

353 g of a 50% solution dodecylbenzenesulfonic acid in isopropanol was slowly added to 189 g of the solution SK50 (0.54 mol) with stirring. To the solution was slowly added while mixing 154 g (0.54 mol) of Tetra(isopropyl)titanate. To the resulting solution was added to 59.8 g (0.40 mol) of triethanolamine, and the pH was increased from 2.5 to about 5. When the addition was completed, the product was mixed for another 5 minutes and then transferred into a sealed container for samples. Then a sample of the product was added to subject the ink composition as described above and then tested for the assessment of activating the adhesion effect, as described above in the test ink. The results are shown in table 2.

Table 2
Adhesion, %
No (comparative)70
Example 6100
Example 7100

Example 8

252 g (0,39 mol SO3H) 50% solution dodecylbenzenesulfonic acid in isopropanol was added to 127 g of a 54% solution of the resin SK in n-propyl (0,39 mol hydroxyl) with stirring. The color of the solution changed from very pale yellow to orange. The solution was allowed to mix for 5 minutes, and then the orange solution was slowly added 110 g (to 0.39 mol) of Tetra(isopropyl)titanate (VERTECTMTIPT, available from Johnson Matthey Catalysts) when mixing. The molar ratio of sulfonic acid to titanium was 1:1. The molar ratio of hydroxyl groups on the resin to titanium atoms was approximately 1:1. When the addition was completed, the product was mixed for another 5 minutes and then was diluted TSDA (trade specific denatured alcohol containing approximately 96% ethanol with n-propanol and ethyl acetate) to obtain a product containing 1,86 wt.% Ti.

Example 9

The procedure of example 8 was repeated, but using only 189 g of a 50% solution dodecylbenzenesulfonic acid isopropane the Les to obtain the product, having a molar ratio OH:SO3H:Ti 1:0,75:1.

Example 10

252 g (0.77 mol SO3H) 100% dodecylbenzenesulfonic acid in isopropanol was added to 254 g of a 54% solution of the resin SK in n-propyl (0.78 mol hydroxyl) when mixing. The color was changed from very pale yellow to brown. The solution was allowed to mix for 5 minutes, and then to the brown solution was slowly added 220 g (0.78 mol) of Tetra(isopropyl)titanate (VERTECTMTIPT, from Johnson Matthey Catalysts) when mixing. The molar ratio of hydroxyl groups of the resin to the sulfonic acid and the titanium was approximately 1:1:1. When the addition was completed, the product was mixed for another 5 minutes. Added TSDA to obtain a product containing 3,71 wt.% Ti.

Example 11

Repeating the procedure of example 10, but TIPT was replaced 177 g (0.78 mol) of tetraethylsilane to obtain a product having a molar ratio OH:SO3H:Ti 1:1:1. Added TSDA to obtain a product containing 2.48 wt.% Ti.

Example 12

Repeating the procedure of example 10, but using a 54% solution of the resin SK in ethyl acetate instead of propyl. The molar ratio of OH:SO3H:Ti in the product was 1:1:1. Added TSDA to obtain a product containing 4,66 wt.% Ti.

Example 13. Test smell

The adhesion promoters were added to test the ink in a concentration of 3 wt.% and on Esenia ink was made from polypropylene film (Propafilm RGP30 OPP from the company Innova Films) using K-bar number 2. The film was dried, making two passes over the silicon bar at 60°C. Then the samples of the film print was stored in sealed glass vessels within 48 hours at 40°C. Then the smell of film print was evaluated by a panel of 5 people on a scale from 1 (no sense of smell) to 4 (very strong smell). The results are shown in table 3.

Example 14. Color test

The adhesion promoters were added to test the ink in a concentration of 3 wt.% and ejecting produced on a polyester film of a thickness of 50 μm Melinex 454 from DuPont Teijin Films using K-bar number 2. The film was dried, making two passes over the silicon bar at 60°C. Measurement Gardner CIELAB was performed using the instrument "color" BYK Gardner. The results are shown in table 3 and represented as values of a and b. A more negative value indicates a green color, and a higher value of b indicates a more yellow color.

Table 3
The adhesion promotersSmellColor
andb
No*2,6-0,58 2,36
VERTEC™ P12*the 3.8-1,444,84
Example 1*2,1-0,692,64
Example 81,5-0,732,61
*indicates a comparative example.

Example 15. Test adhesion

Spent a modified adhesion test, in which samples of the printed ink was allowed to dry at room temperature (about 20°C) instead of drying over the silicon bar at 60°C. In the rest of the test ink, substrate, application method, and method of testing the adhesion of the tape were the same as those described above in the test of adhesion of ink. Printed samples were tested at intervals up to 60 minutes after printing. The results, presented in the form of adhesion in % in table 4 show that the ink containing the adhesion promoters according to the invention, have the same good adhesion, as adhesion measured for ink containing product VERTEC P12, but have much less odor and color. Adhesion is developing rapidly at room temperature, which provides benefits for the printer is.

Table 4
The adhesion promotersWt.% in inkTime after printing (minutes)
15153060
No*-40
VERTEC™ P12*250959598100
VERTEC™ P12*4859598100100
Example 1*28085859090
Example 1* 49095959595
Example 828090909595
Example 8495989898100
Example 927085858585
Example 94859598100100
Example 1029898989898
Example 10498 100100100100
*indicates a comparative example.

1. The adhesion promoters suitable for use in ink formulations for printing to activate the adhesion of printing ink to a substrate, comprising the product of a collaborative interaction:
(a) a solution of a polymer or synthetic resin,
(b) sulfonic acid or a derivative of sulfonic acid and
(c) compounds of a metal selected from one or more of the group consisting of metal halide, metal alkoxide, halide-metal alkoxide or condensed alkoxide of metal, where the metal is selected from titanium or zirconium,
where the number of sulfonic acid or salt of sulfonic acid used in stage (b), and compounds of metal used in stage (C), selected to ensure a molar ratio of the groups SO3X to the atoms of Ti or Zr in the range from 0.25:1 to 2:1, where X represents the atom H or a residue of the base.

2. The adhesion promoters according to claim 1, where the resin is a hydroxyl-containing synthetic resin, which is suitable for use in printing ink.

3. The adhesion promoters according to claim 2, where the hydroxyl-containing resin has a hydroxyl number from about 100 to about 500, in particular from about 200 to p is IMEMO 400 mg KOH/g when tested in accordance with DIN 53240).

4. The adhesion promoters according to claim 1, where the compound of the metal is a titanium alkoxide or zirconium having the General formula M(OR)4in which M is titanium or zirconium, R is alkyl group having 1-8 carbon atoms, and each group R is the same or different from each other group R.

5. The adhesion promoters according to claim 4, where M is titanium.

6. The adhesion promoters according to any one of claims 1 to 5, where the amount of resin used in stage (a), and compounds of metal used in stage (C), provides a molar ratio of HE:the metal atoms in the range from 0.25:1 to 4:1, where the content IT represents a lot of IT is derived from the resin component, calculated based on the hydroxyl number of the resin expressed as mg KOH/g, and metal atoms are atoms of titanium or zirconium obtained from a compound of metal.

7. The adhesion promoters according to claim 1, where the molar ratio of the groups SO3X to the atoms of Ti or Zr is in the range from 0.5:1 to 1.75:1.

8. The adhesion promoters according to claim 1, additionally containing the remainder of the base.

9. The adhesion promoters according to claim 1, additionally containing a solvent or mixed solvent.

10. Printing ink, including:
i) at least one polymeric binder, (ii) a solvent for the polymeric binder, and (iii) AK is ivator adhesion according to any one of claims 1 to 9.

11. The printing ink of claim 10, additionally comprising a dye, pigment or giving the opacity of the substance.

12. The printing ink of claim 10 or 11, where the adhesion promoters are present in a concentration of from 1 to 20 wt.% on the basis of the total mass of the ink.

13. Printing ink according to item 12, where the adhesion promoters are present in a concentration of from 1 to 6 wt.% on the basis of the total mass of the ink.

14. A method of manufacturing a compound that activates adhesion according to any one of claims 1 to 9, including the joint interaction
(i) a solution of a polymer or synthetic resin,
(ii) sulfonic acid or a derivative of sulfonic acid and
(iii) compound of metal selected from one or more of the group consisting of metal halide, metal alkoxide, halide-metal alkoxide or condensed alkoxide of metal, where the metal is selected from titanium or zirconium.

15. The method according to 14, which includes stages:
(a) mixing a solution of a polymer or synthetic resin with sulfonic acid or its derivative and then
(b) mixing the mixture formed in stage (a), with metal connection.

16. The method according to 14, which includes stages:
(a) mixing a solution of a polymer or synthetic resin with metal connection and then
(b) mixing the mixture formed in stage (a), with sulfonic acid or its derivatives.

17. The method according to 14, vkljuchajuwih the stage:
(a) mixing metal link with sulfonic acid or its derivative and then
(b) mixing the mixture formed in stage (a)with a solution of a polymer or synthetic resin.

18. The method according to any of PP-17, additionally comprising a stage of interaction product formed in stage (b), with the basis for the formation of the neutralized or partially neutralized product.

19. The method according to p, where the base includes a metal hydroxide, a compound of Quaternary ammonium or organic amine.

20. The method according to any of PP-17, additionally comprising a stage of mixing the product of stage (b) with a solvent.

21. The method according to p or 19, further comprising a stage of mixing the neutralized or partially neutralized product with a solvent.

22. The method according to 14, where the sulfonic acid or its derivative is mixed with a solvent or dissolved in it before mixing with other reagents.



 

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EFFECT: use of disclosed dustless pigment composition in printing ink enables to obtain prints with high resistance to wet treatment.

16 cl, 1 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: invention relates to reactive metal-complex azo dyes, specifically to reactive dyes of formula where R1 is hydrogen, (R2)5 is a nitro group, X is chlorine, T is a radical of formula , ,

or

,

where (R3)0-2 -0, Z is a vinyl or -CH2-CH2-U, U is a group removable in an alkaline medium, Q - -CH(Hal)-CH2-Hal or -C(Hal)=-CH2, Hal is a halogen, s equals 0 or 1.

EFFECT: disclosed dyes have high resistance to wet processing, especially when dyeing or printing synthetic polyamide fibre materials.

7 cl, 12 ex

FIELD: chemistry.

SUBSTANCE: invention relates to compositions for marking substrates. The invention describes a composition for marking substrates, which contains 0.01-50 wt % colourant, 0.01-50 wt % metal salt and carboxylic acid, 1-80 wt % binder and 1-99 wt % organic solvent. Also described is a method of preparing the said composition, a substrate coated with the said composition and a method of marking substrates using the said compositions. The disclosed composition is based on using readily accessible carboxylic acid salts which can not be coloured before exposure to effects of energy.

EFFECT: composition enables to obtain semi-transparent or transparent coatings with high intensity and brightness.

9 cl, 14 ex

FIELD: printing.

SUBSTANCE: there is described composition of inks for jet printers including jet forming thinner, containing organic cosolvents, surfactant and buffer solution, the set of solid pigments samodispergirovannyh in this diluent, and a complex poluefir and styrene maleic anhydride (SMA), dispersed in this diluent. System for printing images on a substrate is also described, including the printing head, filled with inks able to form jet.

EFFECT: offered inks provides decrease in a time of drying at achievement of a sharp image and decrease in quantity of surfactants or wetting agent or their absence in inks on the basis of black pigment.

10 cl, 5 dwg, 3 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to liquids for holding aqueous ink on paper for jet printing. A liquid is described for holding water-based ink onto paper, containing a non-curling co-solvent in form of an inner salt, with a sp3-hybrid nitrogen cation and associated anionic charge, insulated on the oxygen anion, directly bonded to the sp3-hybrid nitrogen cation, or insulated between oxygen atoms of a carboxylate group, and is a compound which contains a group chosen from ammonium-N-oxide, N, N, N-trimethylglycinate and amino acid. Described also is use of the said liquid for holding ink on paper to prevent paper from curling during printing.

EFFECT: obtaining liquid for holding water-based ink onto paper, which efficiently reduces curling and deformation of printing paper.

14 cl, 9 tbl, 7 ex

FIELD: physics; image processing.

SUBSTANCE: present invention pertains to a protective element for counterfeit protected paper, valuable documents etc. as well as the counterfeit protected paper and valuable documents, method of making such a protective element, printing ink containing pigment with variable optical properties and method of making such printing ink. The protective element contains a thin-layer element with a colour tilt effect, consisting of a reflecting layer, absorbing layer and an intermediate layer between the reflecting layer and the absorbing layer. The intermediate layer is formed by the printing layer, containing dispersed particles with monomodal or oligomodal size distribution.

EFFECT: obtaining a simple protective element which can be made cheaply and which has high level of security from counterfeit.

62 cl, 12 dwg

FIELD: printing technology.

SUBSTANCE: paint for ink-jet printing contains synthetic food colourant, glycerin and sodium dodecylbenzenesulfonate as surface active substance, sorbit acid as preservation agent, liquid ammonia, isopropyl alcohol and distilled water. Environmentally clear, affordable and cheap components are used as painting ingredients.

EFFECT: four-colour printing with fast paint setting on paper; compatibility with any printing units and prevention of contacting printing units damage.

1 tbl, 3 ex

FIELD: technological processes.

SUBSTANCE: material marking method consists in the fact that there made is paint consisting of binding agent and fine microparticles and/or microencapsulated microdrops having diameter of approximately 40 to 80 mcm. Then, the mark having surface area of about one square centimetre and containing serial registration number is printed on the product by using the above paint. The above mark is lit with the light and chaotic character of distribution, shape and sizes of fine microparticles and/or microencapsulated microdrops are fully flashed; due to which non-reproducible and distinctive background card for the introduced mark is created. And data reads composed of the above background card are subject to filtration by using stop-down lens serving for neutralisation and suppression of any possible reflection of distortion of and damage to patterns, and then the above data reads subject to filtration are identified by means of optic-digital video camera interrelated with software, and view finder. At that, video camera has the possibility of transmitting the data to registration database for further comparison and confirmation of authenticity of the product marked in such a manner.

EFFECT: marking method allows high degree of protection of the product against false fabrication and copying.

10 cl, 2 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: disclosed is a colourless luminescent decorative paint containing a luminophor and binder. The luminophor is an organic luminophor with anomalously large Stokes shift which is greater than 100 nm, which is colourless in daylight and luminescent in the visible spectral region when illuminated with a source of UV radiation. The organic binder is a transparent organic substance which does not absorb long-wave ultraviolet radiation in the 365-420 nm range.

EFFECT: obtaining fast and stable luminescent paint which contains a colourless organic luminophor, which enables to create a latent image which appears upon illumination with UV radiation which is invisible in daylight as well as in the dark, in the absence of UV radiation, the paint ensures high strength of the polymer base of the decorative layer of the article obtained using said paint.

13 cl, 8 ex

FIELD: printing industry.

SUBSTANCE: ink that contains water, water-insoluble colour and multiple water-soluble organic dissolvents is applied onto a carrier. Specified dissolvents contain a good solvent for the specified colour (A) and a poor solvent for the specified colour (B) with the ratio of A to B, equal from 10:5 to 7:9. The water-soluble organic dissolvent that has maximum value Ka, identified by Bristow method, among all water-soluble organic dissolvents in the ink, relates to poor dissolvents.

EFFECT: high extent of surface coating and high density of OD image even with small quantity of ink.

3 cl, 16 dwg, 11 tbl, 16 ex

FIELD: printing industry.

SUBSTANCE: ink contains a liquid carrier, which includes water, an organic dissolvent and an organic amine, selected from 2-amino-2-methyl-1-propanol, 2-dimethylamino-2-methyl-1-propanol, diethanolamine and their mixtures; and a dye of an acid-sensitive pigment, encapsulated into a polymer, which is a copolymer of sterol, acrylic acid and methacrylic acid or its ether, dispersed in the liquid carrier. Also an ink set is described for jet printing, as well as a method to print images with application of the specified ink.

EFFECT: improved quality of images both on glossy surface and on plain paper.

14 cl, 6 tbl, 6 ex

FIELD: printing industry.

SUBSTANCE: dye composition for jet recording is proposed, containing a ground pigment, a surfactant and a system of non-aqueous dissolvents. The system of non-aqueous dissolvents includes 1) from around 50 wt % to around 95 wt % of the main system of co-solvents, selected from a group of ethers of propylene glycol, acetates of glycol ether, ketones and esters, having surface tension of less than 32 dyne/cm (32x10-5 N/cm) at 25°C; 2) from around 1 wt % to around 30 wt % of the second system of co-solvents selected from a group of n-ethyl pyrrolidone, propylene carbonate, N-methyl pyrrolidone, methyl ester of lactic acid, 1,3-butanediol and glyceryl acetate, having surface tension of more than 32 dyne/cm (32x10-5 N/cm) at 25°C; 3) from around 1 wt % to around 10 wt % gamma-butyrolacton; 4) at least 2 wt % of resin dissolved in the dye composition. Also a group of dyes is proposed, containing the specified dye composition, as well as a method of images printing.

EFFECT: higher speed of dye drying, its stability to fading and improved spreading of a raster dot.

13 cl, 7 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to ink systems for jet printing, containing a fixing composition with low corrosion activity. The invention discloses a fixing composition for jet printing, containing water or a mixture of water and at least one water-miscible organic solvent, and a polycationic fixing agent whose counterion is not a halogen, where the counterion is selected such that it reduces availability of the halogen in the fixing agent. The invention also discloses a method of applying an essentially noncorrosive ink composition and a jet system for providing ink with low corrosion activity.

EFFECT: invention reduces the negative effect of the fixing agent on components of the printing head while preserving all its useful properties.

10 cl, 2 dwg

Protective element // 2419549

FIELD: printing industry.

SUBSTANCE: invention relates to a thermochromic printing ink for gravure printing, to a data carrier with a printed image made by the gravure printing method using such a printing ink, and also to method of making such a printing ink and the specified data carrier. The thermochromic printing ink for gravure printing contains a microcapsulated three-component mix with a weight ratio from 25% to 40%, made of at least one electron donor, at least one donor acceptor and at least one dissolvent.

EFFECT: proposed thermochromic printing ink provides for generation of image with fine linear pattern and a microtext, which is characterised by easily distinguishable thermochromic effect and a convex shape, which develops a counterfeit protection effect.

21 cl, 3 dwg, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a coating composition for making substrates, preparation thereof and use, which contains colour-forming substance, polymer binder, solvent, additional components and a salt of an organometallic compound with an amine of formula where X is Si or B, R3, R4 and R5 denote H, alkyl, allyl, or R3 and R4 together with a nitrogen atom form a morpholine ring; o and p = 0 or 1, E and F are selected from R6 and R7 = H, R1 is phenyl or R1 together with R2 form a residue selected from

EFFECT: obtaining novel compositions for producing substrates and marking substrates.

13 cl, 13 ex

FIELD: chemistry.

SUBSTANCE: invention describes a dustless powdered pigment composition which is essentially free from binder substances and contains: at least 60 wt % of at least one nacreous pigment, 1-15 wt % non-ionic monomeric wetting substance and/or polysiloxane-based non-ionic wetting substance and 1-39 wt % solvent or mixture of solvents, wherein the total amount of separate components equals 100 wt %. Said non-ionic wetting substance contains OH groups and has hydroxyl number from 30 to 150 mg KOH/g of wetting substance, preferably from 50 to 120 mg KOH/g of wetting substance. The invention also describes a method of preparing the pigment composition and use thereof.

EFFECT: use of disclosed dustless pigment composition in printing ink enables to obtain prints with high resistance to wet treatment.

16 cl, 1 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: invention relates to reactive metal-complex azo dyes, specifically to reactive dyes of formula where R1 is hydrogen, (R2)5 is a nitro group, X is chlorine, T is a radical of formula , ,

or

,

where (R3)0-2 -0, Z is a vinyl or -CH2-CH2-U, U is a group removable in an alkaline medium, Q - -CH(Hal)-CH2-Hal or -C(Hal)=-CH2, Hal is a halogen, s equals 0 or 1.

EFFECT: disclosed dyes have high resistance to wet processing, especially when dyeing or printing synthetic polyamide fibre materials.

7 cl, 12 ex

FIELD: chemistry.

SUBSTANCE: composition contains a mixture of polyamide, where the ratio of terminal amino groups in the terminal carboxyl groups of the polyamide polymer is less than 0.2, polyester which is capable of crystallising and an interfacial tension reducing agent.

EFFECT: composition enables to obtain dispersed particles with average size of less than 200 nm when stretched, good colour composition which will not exhibit high increase in turbidity with increase in the amount of dispersed material, or has acceptable turbidity during production, and has good colour, especially in the absence of cobalt.

7 cl, 3 tbl, 18 ex, 8 dwg

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