Novel photoinitiators

FIELD: chemistry.

SUBSTANCE: invention relates to a photoinitiator, a method for production and use thereof and a coating composition. The photoinitiator is a compound of formula: (PI-Sp)n-BB (I), where PI is a thioxanthone group, optionally including additional substitutes in the Sp group; Sp is a spacer link selected from a group consisting of or , BB is a backbone chain link selected from a group consisting of

The method of producing the photoinitiator includes the following steps: (a) optionally substituted thioxanthone, containing at least one hydroxy group, reacts with epichlorohydrin or haloacetic acid ester; (b) the compound from step (a) reacts with the corresponding backbone chain link containing a functional group, or the compound from step (a) reacts with a compound containing a functional group, and the obtained intermediate then reacts with the corresponding backbone chain link; optionally (c) obtaining derivatives of the compounds from step (b). The photoinitiator is used to cure a coating composition, preferably printing ink containing a polymerisable component.

EFFECT: invention enables to obtain a photoinitiator with good curing activity, faint odour and good compatibility with other components of the composition.

10 cl, 1 tbl, 4 ex

 

The technical field to which the invention relates.

The present invention relates to new compounds which are applicable as photoinitiators in coating compositions, preferably inks.

The level of technology

Radiation curable compositions, such as compositions, UV-curable, usually include photoinitiator to start/amplification reaction polymerization, the polymerized material, which typically contains Ethylenediamine group. Such photoinitiator must possess good activity curing, low odor and good compatibility with other components of the composition of the coating. Particularly for use in packaging food products increased legal requirements that must be met for photoinitiator. In addition, photoinitiator should be available at a reasonable or cheap price.

Accordingly, research is ongoing in recent years to develop new photoinitiators meeting the above requirements. For example, in WO 03/033492 described a number of photoinitiators.

Disclosure of inventions

The aim of the present invention was the development of new photoinitiators meeting the above requirements.

It was achieved according to the present invention a number of photoinitiators, in accordance with the definition of the Institute of economy and management in the claims. In particular, the present invention relates to photoinitiators formula (I)

where PI is a group of thioxanthone, optionally including additional substituents in addition to the Sp group

Sp is a spacer elements linkage selected from the group consisting of

where

PI is a group of thioxanthone, optionally including additional substituents in the Sp group

Sp is a spacer elements linkage selected from the group consisting of

or

BB is a link in the main chain selected from the group consisting of

,

where

R2and R3are identical or different and denote H, optionally substituted linear or branched C1-8the alkyl residue or an acyl residue;

R4is H or hydroxy group;

R5is H or C1-4-alkyl;

R6and R7are identical or different and denote H, optionally substituted linear or branched C1-8the alkyl residue;

A is NR8where R 8is H, optionally substituted linear or branched C1-8alkyl residue or acyl residue, or an optionally substituted residue C1-8the alkylamine;

R9is H or C1-4-alkyl;

p is an integer of 1-10, preferably 3-6;

q is an integer 3-12;

r is in the range 2-3;

w is an integer of 2-15, preferably 3-10;

and n is 1 or 2.

In the description of the link group which is not attached to an atom of this group should be considered as a link connecting this group with the corresponding other group of photoinitiator.

The present invention reveals new patterns of photoinitiators. Unexpectedly it was found that the new compounds of the present invention are suitable photoinitiators. It was impossible to foresee from materials WO 03/033492, which is restricted to certain structures. Thus, the present invention significantly extends the range of compounds that can be considered as photoinitiator in coating compositions, preferably inks.

According to a preferred implementation of the present invention, it was unexpectedly found that it is also possible to introduce amino groups into the main chain of photoinitiators, and that these amino amine enhance the character of the sticks curing compounds of the present invention. Amino group, most preferably are tertiary amine groups. According to the present invention, the amino group can be part of the main chain of the compounds of the present invention, or alternatively, they may be introduced into compounds as side or end groups.

According to another implementation of the present invention also proposes a future free from nitrogen photoinitiator also with good curing characteristics and compatibility. These are free from nitrogen photoinitiator include free hydroxyl group. Unexpectedly, it was found that these compounds also have good curing characteristics and compatibility, but can be optionally bound with a resin binder (for example, by reaction of the free hydroxyl groups with isocyanate groups). This prevents the release of such photoinitiators of the composition and thus eliminates low odor composition and minimizes the risk of migration of the coating film.

According to the present invention PI is thioxanthones.

According to the present invention, it was found that photoreaction activity of these compounds is best when the group Sp linking group of thioxanthone polymer main chain, is in the 2nd position in the ring of thioxanthone.

Unlike rscr the party WO 03/033492 unexpectedly, it was found, what photoreaction activity of the compounds of the invention can be increased if there is at least one, preferably one or two, additional Deputy, next to the group Sp group PL. According to the most preferred implementation, it was determined that additional Deputy, in particular, C1-4alkyl group, preferably a metal or ISO-propyl group, especially of the isopropyl group in position 4 groups of thioxanthone, have a positive effect.

Thus, according to the preferred implementation of the present invention, PI group substituted by at least one, preferably one or two residues selected from the group consisting of linear or branched C1-4the alkyl, preferably linear or branched C1-4of alkyl, linear or branched C1-8alkoxygroup, preferably linear or branched C1-4alkoxygroup or halogen, preferably Cl. Linear or branched C1-8alkyl, preferably linear or branched alkyl residue C1-4especially preferred.

The synthesis of substituted thioxanthones well-known specialists in this field of technology. Commercially available several substituted thioxanthones.

According to a preferred implementation of the present from which retene, substituted thioxanthone get a reaction thiosalicylic acid (commercially supplied, for example, Sigma Aldrich) with appropriately substituted derivatives of phenol. For example, the synthesis of 2-hydroxy-4-isopropylthioxanthone carried out in the following way:

The reaction is performed in the presence of a strong acid, such as concentrated sulphuric acid when heated to about 60-100°C.

Spacer elements links can be attached to a group of thioxanthone or acridone known reactions.

Spacer elements element

can be formed by reaction of a derivative of 2-gidrometeotsentra with epichlorohydrin followed by reaction with the nucleophilic group (Nu) of the link core circuit CC:

Nu is a hydroxy or amino group.

Spacer elements element

can be easily obtained by the reaction of a derivative of 2-gidrometeotsentra with the derived halogenases acid, such as ethyl ether bromoxynil acid and subsequent reaction with the nucleophilic group (Nu) of the link core circuit CC:

Nu is a hydroxy or amino group.

Also known reaction between a derivative of α-halogencarbonic acid and hydro is sisterhen connection. Usually it is carried out by heating in the presence of base, such as sodium hydroxide.

As described above, according to a particularly preferred implementation of the present invention, the link core circuit includes at least one amino group. It was unexpectedly found that such compounds are not only good photoinitiator, which in itself is not predicted, but that the introduction of such amino groups resulted in increased photoreactions activity of the compounds.

According to a particularly preferred implementation of the present invention, such an amino group is a tertiary amino group.

A preferred group of compounds specified implementation is characterized by the formula

where

R1is H or a linear or branched C1-8-alkyl, preferably linear or branched C1-6-alkyl, most preferably CH3C2H5N-C3H7ISO-C3H7H4H9, sec-C4H9, tert-C4H9,

EXPLOSIVES are selected from the group consisting of

where

R2and R3are identical or different and denote H or O

where

R6and R7independently are H Il is a linear or branched C 1-8-alkyl, preferably linear or branched C1-6-alkyl, most preferably CH3C2H5N-C3H7ISO-C3H7H4H9, sec-C4H9, tert-C4H9; and

p is an integer of 1-10, preferably 3-6, most preferably 3-5;

q is an integer of 3-12, preferably 9;

A is NR8where R8is H, linear or branched C1-4alkyl residue, residue C1-4the alkylamine or

where R6and R7such as defined above;

R4are H or hydroxy-group;

R5is H or CH3; and

n is 2.

In this group of compounds of the functional amino group can be in the main chain as side or end groups.

Link PI-Sp used in the description, is

the synthesis of which was described above.

The links of the main chain

obtained from commercially available polyoxypropyleneamine, such as Jeffamine D230 or Jeffanine D400.

The links of the main chain

easily obtained first by the interaction of the amino group with the link of PI-Sp, with subsequent reaction of the free amino groups, for example with polyoxyethylenated, to the to shown to get the next connection:

Preferred examples of compounds of this group:

Source material the main chain: Jeffamine D230 or Jeffamine D400

Source material the main chain: Jeffamine D230

Another preferred group of compounds of the present invention is characterized by the formula

where

EXPLOSIVES are selected from the group consisting of

where

q is an integer 3-12, p is edocfile 9;

R5is H or CH3;

R6and R7independently are H or linear or branched C1-8-alkyl, preferably linear or branched C1-6-alkyl, most preferably CH3C2H5N-C3H7ISO-C3H7H4H9, sec-C4H9, tert-C4H9;

w is an integer of 2-15, preferably 3-10,

n is 1 or 2.

Link PI-Sp, which is used in the description, is

the synthesis of which was described above.

The link in the main chain Of

obtained by the interaction of the corresponding link of the PI-SP with polytetrahydrofuran and then with the derived 4-aminobenzoyl. The link in the main chain

obtained by the interaction of the corresponding link of the PI-Sp with polyoxyethylenesorbitan or Polyoxypropylenediamine and then with the derived 4-aminobenzoyl.

Preferred examples of compounds of this group are:

Another preferred group of compounds of the present invention is characterized by the formula

where

R10and R11are the same or different and mean H, CH3or CH(CH3)2;

EXPLOSIVES are selected from the group consisting of

where

q is an integer of 3-12, preferably 9;

R5is H or CH3;

R6and R7independently are H or linear or branched C1-8-alkyl, preferably linear or branched C1-6-alkyl, most preferably CH3C2H5N-C3H7ISO-C3H7H4H9, sec-C4H9, tert-C4H9;

R9is N or CH3;

r is in the range 2-3;

n is 2.

Link PI-Sp, which is used in the description, is

the synthesis of which was described above.

In the first main circuit of the above list polyol is a polyol-based pentaerythritol.

According to the present invention, the polyol-based pentaerythritol is a polyol, including a Quaternary carbon atom, and p is at least three of the hydroxy-group. A preferred example is a polyol 3380:

In a commercial product Polyol 3380 r statistically 2.5.

Of course, other polyols with three or more hydroxyl groups can also be used as polyol 3380, in accordance with the present invention.

Depending on the relationship of the source components one, two or all three of the hydroxy-group of the polyol 3380 can interact with a group of PI-Sp. The remaining free hydroxy-group of the polyol 3380 can react with the terminal groups, for example dialkylaminomethyl group.

Another link in the main chain of the above list obtained by the interaction of the corresponding link of the PI-Sp with polyoxyethylenesorbitan or polyoxypropyleneglycol.

Preferred examples of compounds of this group are:

source material the main chain: DER 732 (Dow)

The above photoinitiator can be added to conventional radiation curable coating compositions. Such compositions of the coatings are widely known in modern art and need not repeat in detail.

The composition of the coating, including photoinitiator of the present invention will typically include at least one happy is azione-curable monomer and/or oligomer, photoinitiator of the present invention and optional additional reactive diluent. In the case of printing ink composition will also contain a colorant, such as pigment.

Radiation-curable monomer or oligomer is preferably ethyleneamines connection. Examples of suitable acrylate oligomers include aliphatic or aromatic urethane acrylates, polyether acrylates, acrylates complex polyester and epoxyacrylate (such as epoxyacrylate bisphenol A). Examples of suitable acrylate monomers include hexaniacinate, trimethylolpropane, di-trimethylolpropane, di-pentaerythritoltetranitrate, polyether acrylates, such as ethoxylated trimethylolpropane, triacrylate of propoxylated glycerol, ethoxylated pentaerythritoltetranitrate and epoxyacrylate, such as diamondigital (=2,2-bis[4-(2-hydroxyethoxy)phenyl]propanediamine, Ebecryl 150 from UCB) and glycosidically, such as glycolylneuraminic).

A great advantage of the present invention is the fact that most photoinitiators described in the application, contain the amino group in their molecules. Thus, the number of additional auxiliary means can be greatly reduced or even some of the applications that are completely excluded. In addition, any release of small molecules specified excipients of the final coating significantly reduced, which leads to the reduction of environmental problems. However, to use photoinitiators of the present invention that do not contain in the molecule of the amino group, the compounds of this design preferably contain auxiliary substances, such as aminoaryl or ester dimethylaminobenzoyl acid, known in modern technology. Preferably auxiliary substance will be aired dimethylaminobenzoyl acid in the case of printing ink or aminoacylation in the case of varnish. Some inks, such as those used in flexo printing, may contain both types of amines.

Multifunctional initiators of formula (I) are particularly suitable for the ink, in particular printing inks, including lithographic ink. They usually include as additional components to the above, one or more pigments, waxes, stabilizers and regulators fluidity, for example, as described in "Handbook of printing inks", fourth edition, Leach, BC and others (Leach, R.H. (ed), Van Nostrand Reinhold, Wokingham, (1988), the disclosure of which is included in the description by reference. Photoinitiator of the present invention have good compatibility with the other component and songs.

The present invention will be further described with regard to the non-limiting examples.

The implementation of the invention

Example 1. Synthesis of derivatives of thioxanthone

The overall synthesis process NTH intermediates containing hydroxyl, perform the following way: thiosalicylic acid (0.1 mol) is added slowly to 150 ml of concentrated sulfuric acid and the mixture is stirred for 5 minutes to ensure complete mixing. Derivatives of phenol (0.5 mol) is added slowly to stir the mixture for 30 minutes After the addition, the reaction mixture was stirred at room temperature for 1 h and then at 80°C for 2 h and then left overnight at room temperature. The resulting mixture is carefully poured under stirring in 10-fold excess of boiling water and then further boiled for 10 minutes the Solution is cooled and filtered. The residue is recrystallized from a mixture of dioxane-water. Gidrometeostantsy carefully characterize and determine the FT-IR with Fourier transformation) and NMR.

The above method are the following gidrometeostantsy

Example 2. Obtaining jingle is in PI-Sp

Example 2a. Intermediates acid-thioxanthen

Synthesis of intermediates acid-thioxanthen shown in the example of synthesis of 4-isopropyl-2-carboxymethyl-hydroxy-thioxanthone:

2.4 grams of sodium hydroxide is refluxed in 40 ml of tetrahydrofuran (THF) 5 minutes 4-Isopropyl-2-gidrometeocenter (2.7 g of 0.01 mol) is added and continue boiling under reflux for 1 h, during which time the color changes to red, indicating the formation of the sodium salt of 4-isopropyl-2-gidrometeotsentra. Add ethylbromoacetate (3.51 g, 0,021 mol), continue boiling under reflux 5 h, at which the color of the solution changed to yellow. After cooling to room temperature, add 40 ml of water, and the THF is distilled off to obtain a clear red solution. The solution is refluxed an additional 3 h to gidrolizirovanny all intermediates of ester. Then the solution is cooled to 50°C and add 40 ml of 1.0 M hydrochloric acid, the precipitated solid product. Then refluxed an additional 10 minutes for the final conversion of all the sodium salt to the free acid, the solution is cooled to room temperature and stirred for 2 h before filtering solids, washed with 40 ml of water and dried in a vacuum Cabinet at 80°C. Yield stood at the focus of about 95%.

Other intermediates used acid-thioxanthen get in the same way, starting from the corresponding derivative of thioxanthone.

Example 2b. 2 Carboxymethyloxysuccinic

2 Carboxymethyloxysuccinic can be synthesized by one-step reaction: thiosalicylic acid (0.1 mol) is added slowly to 150 ml of concentrated sulfuric acid and the mixture is stirred for 5 minutes to ensure complete mixing. Phenoxyethanol acid (0,5 mol) is added slowly to stir the mixture for 30 minutes After the addition, the reaction mixture was stirred at room temperature for 1 h and then at 80°C for 2 h and then left overnight at room temperature. The resulting mixture is carefully poured under stirring in 10-fold excess of boiling water and then further boiled for 10 minutes the Solution is cooled and filtered. The residue is recrystallized from a mixture of dioxane-water.

Example 2c. Intermediates epoxy-thioxanthone

The General process for the synthesis of intermediates of the epoxy-thioxanthen the following: a mixture of hydroxyltoluene (0,03 mole), epichlorohydrin (20 ml), powdered anhydrous potassium carbonate (6.5 g), toluene (30 ml) and polyethylene glycol (PEG-400, 0.5 ml) is stirred for 2 h at 80°C and then refluxed 2 h at 135°C. the Organic layer after cooling, if the indicate, and the inorganic residue was washed with toluene until the discoloration of the solution. The combined solution is distilled to remove solvent and excess epichlorohydrin, and the residue extracted with a mixture of chloroform and water in a separating funnel. The solution in chloroform, dried with anhydrous calcium chloride and evaporated. The crude product is recrystallized from a mixture of toluene-ethanol (V/V=6/1).

Other intermediates used epoxy-thioxanthone get in the same way, starting from the corresponding derivative of thioxanthone.

Example 3. Getting photoinitiators

Example 3.1. Synthesis

of 0.01 Mole of 4-methyl-2-epoxytetradecane (obtained in accordance with example 2 (C) and 0.04 mol of Propylamine (RA) was dissolved in 20 ml of chloroform, and the mixture was stirred at 40°C for 12 hours. Unreacted RA and the solvent, chloroform removed by rotary evaporation to obtain 4-methyl-2-(1-propyl-amino-2-hydroxy)-propositionthe (METH-RA). 0,005 Mol RE (polyoxyethylenated) and 40 ml of ethanol is added to the flask containing METH-RA. The mixture is refluxed at 80°C for 8 hours in an atmosphere of N2. The solvent, ethanol is removed by a rotary evaporation to obtain specified in the connection header.

In a similar manner using other amines, such as PIP is Razin, can be obtained more photoinitiator containing amino groups in the main chain.

In the case of the use of polymeric amines, such Jeffamines, there is no need to add polyalkoxy connection.

Example 3.2. Synthesis

2 Carboxymethyloxysuccinic (2,88 g of 0.01 mol, obtained in accordance with example 2b), poly(THF) 650 (6.50 g, of 0.01 mol), 4-dimethylaminobenzoyl acid (2 g, 0,012 mol), 0.3 g of p-toluensulfonate acid and 100 ml of xylene is added in the three-neck flask equipped with input of nitrogen and trap Dean-stark. The solution mixture is subjected to the azeotropic distillation at 150°C for 12 h and then distilled xylene. The mixture is then heated to 200°C for 5 h, and then cooled to 80°C. Then, while stirring, 100 ml of toluene. The solution is cooled to ambient room temperature, then filtered and washed twice with 100 ml of 0.25 M sodium hydroxide and twice with 100 ml water. The organic phase is dried with anhydrous magnesium sulfate, and the solvent is removed using a rotary evaporator to obtain a red oil. The output is around 86%.

In a similar manner using other polyalkoxy compounds, such as polyoxyethylenated or Polyoxypropylenediamine, can be obtained more photoinitiator, including terminal amino group.

In SL the tea of the use of polymeric amines, such Jeffamines, there is no need to add polyalkoxy connections.

Example 3.3. Synthesis

Placed in a flask with 0.2 mole of 2-carboxymethylcysteine (obtained in accordance with example 2b) and 0.1 mol of REO 526 (polyoxyethylenated). The mixture is heated to 150°C for 12 h and then to 180°C for 6 h to obtain specified in the connection header. The yield is about 100%.

Example 3.4. Synthesis

This compound is synthesized in the same manner as in example 3.3, but using epoxy resin DER 732, supplied by Dow instead REO 526.

It should be understood that other compounds of the present invention can be obtained in a similar manner using the appropriate source or intermediate materials. Optional minor changes in the reaction conditions do not go beyond the common practice of specialists in this field of technology.

The reaction of obtaining derivatives (such as etherification of the free hydroxy groups or transferring of free amino groups in amides) can be performed in accordance with standard procedures that do not require a detailed description in the application.

Example 4. Getting ink

a) Ink with listeriosis photoinitiation

Printing ink, get mixing the usual way following components:

Componentwt. -%
Ebecryl 657 (Preferablyat)30
Ebecryl 1608 (Epoxyacrylate)22,3
TMRCA (Monomer)20
Photoinitiator (example 3.2)8
Speedcure EDB (Ethyldimethylamine, Supplement)1,2
Florstab UV 1 (Stabilizer)0,5
Ciba Irgalite GLO (Pigment PB 15:3)18

Inks have good curing properties without requiring the use of additional auxiliary amine.

b) Ink without aminobenzamide of photoinitiator

Printing ink is produced by mixing the usual way following components:

Componentwt. -%
Ebecryl 657 (Preferablyat)30
Ebecryl 1608 (Epoxyacrylate)23,5
20
Photoinitiator (example 3.3)4
Speedcure EDB (Ethyldimethylamine, Supplement)4
Florstab UV 1 (Stabilizer)0,5
Ciba Irgalite GLO (Pigment PB 15:3)18

Inks show good curing properties.

Test method

a) Test spirostanol film

On a plastic substrate standard imprint placed alongside a sample of the coating composition of the present invention. The cure perform mercury lamp (160 W/cm, conveyor speed of 30 m/min). Simultaneously execute the application on the plastic film, including standard and subjects ink. Cotton cloth soaked in alcohol, the ink film is treated to extinction. The number of double cycles of abrasion, which are necessary for this, given the degree of cure.

b) Limit the curing

The ink of the present invention to imprint on the plastic substrate on the machine Little Joe or PrufBau to 1.50 g/m2. Several parts of the printing utverjdayut. Each part serves a UV dryer with conveyor speed is gradually decreased at each sample. Check at the touch of a thumb, overiden plank is or not. Otherwise, the speed reduce and serves a different part of the print and again appreciate the cure. At lower speed, the irradiation is sufficient to fully cure the ink and the thumb is no longer leaves marks on the print. Then register the speed of the dryer and is considered the "limit curing" (m/min). The higher the number, the higher reactivity of the ink.

The following table summarizes the results of the test limit curing several ink of the present invention, including various photoinitiator of the present invention in comparison with the product comparison Omnipol TX (WO 03/033492, approx. 3). The ink receiving in accordance with example 4 (ink according to comparative example 1 (1) are obtained according to example 4b using 3% of the mass. Omnipol TX and respectively 24.5% of the mass. Ebecryl 1608):

It was shown that the ink of the present invention have comparable or better amount of curing than in comparative example Omnipol TX. In addition, in the case of example 1, the number of additional excipients could be significantly reduced, which lowers the complexity with the separation caused by the auxiliary substance.

c) Blocking test

Smear the ink of the present invention relative to the standard to be applied on the porous paper (copier the local machine). Parameter curing is 1 passage 120 m/min, the minimum lamp power. The seal can withstand relatively clean part of the porous paper under pressure (10 tons) at room temperature for 30 seconds. The results are expressed function blocking level, and gives an estimate of the surface hardening.

d) the relative Reactivity of polyurethanes with terminal isocyanate groups

To show that certain ink of the present invention, which contain free hydroxyl groups can be grafted onto a suitable resin binder, the ink according to example 4b), but containing photoinitiator according to example 3.4, added to the polyurethane containing free isocyanate end groups. After a reaction time of 2 h at 70°C can be observed a marked decrease in the content of free isocyanate groups.

Such ink, but containing Ominipol TX, under the same conditions, does not react with the specified polyurethane containing free isocyanate end groups.

1. Photoinitiator formula (I)

where
PI is a group of thioxanthone, optionally including additional substituents in the Sp group;
Sp is a spacer elements linkage selected from the group consisting of

BB is a link in the main chain, using the data from the group consisting of







where R2and R3are identical or different and denote H, optionally substituted linear or branched C1-8the alkyl residue or an acyl residue;
R4is H or hydroxy-group;
R5is H or C1-4-alkyl;
R6and R7are identical or different and denote H, optionally substituted linear or branched C1-8the alkyl residue;
A is NR8where R8is H, optionally substituted linear or branched C1-8alkyl residue or an optionally substituted residue C1-8the alkylamine or

where R6and R7such as defined above;
R9is H or C1-4-alkyl;
p is an integer of 1-10, preferably 3-6;
q is an integer 3-12;
r is in the range 2-3;
w is an integer of 2-15, preferably 3-10;
and n is 1 or 2.

2. Photoinitiator according to claim 1, in which the Sp group is associated with the PI group of thioxanthone in the 2nd position.

3. Photoinitiator according to claim 1, in which the PI group substituted by at least one, preferably 1 or 2 residues selected from the group consisting of linear or branched C1-8the alkyl, preferably linear or branched C1-4of alkyl, linear or branched C1-8alkoxygroup, preferably linear or branched C1-4alkoxygroup or halogen, preferably Cl.

4. Photoinitiator according to claim 3, in which position 4 groups PI has a linear or branched C1-8the alkyl residue, preferably a linear or branched C1-4the alkyl residue.

5. Photoinitiator according to claim 1, formulas

where
R1is H or a linear or branched C1-8-alkyl, preferably linear or branched C1-6-alkyl, most preferably CH3C2H5H-C3H7ISO-C3H7H-C4H9, sec-C4H9, tert-C4H9,
EXPLOSIVES are selected from the group consisting of


where
R2and R3are identical or different and denote H or

where
R6and R7independently are H or linear or branched C1-8-alkyl, preferably linear or branched C1-6-alkyl, most preferably CH3C 2H5H-C3H7ISO-C3H7H-C4H9, sec-C4H9, tert-C4H9;
p is an integer of 1-10, preferably 3-6, most preferably 3-5;
q is an integer of 3-12, preferably 9;
A is NR8where R8is H, linear or branched C1-4alkyl residue, residue C1-4the alkylamine or

where R6and R7such as defined above;
R4are H or hydroxy-group;
R5is H or CH3;
n is 2.

6. Photoinitiator according to claims 1 to 4, the formula

where
EXPLOSIVES are selected from the group consisting of



where
q is an integer of 3-12, preferably 9;
R5is H or CH3;
R6and R7independently are H or linear or branched C1-8-alkyl, preferably linear or branched C1-6-alkyl, most preferably CH3C2H5H-C3H7ISO-C3H7H-C4H9, second-From4H9, tert-C4H9;
w is an integer of 2-15, preferably 3-10,
n is 1 or 2.

7. Photoinitiator according to claims 1-5, the formula

where
10and R11are the same or different and mean H, CH3or CH(CH3)2;
EXPLOSIVES are selected from the group consisting of


where q is an integer of 3-12, preferably 9;
R5is H or CH3;
R6and R7independently are H or linear or branched C1-8-alkyl, preferably linear or branched C1-6-alkyl, most preferably CH3C2H5H-C3H7ISO-C3H7H-C4H9, sec-C4H9, tert-C4H9;
R9is H or CH3;
r is in the range from 2 to 3;
n is 2.

8. The method of producing photoinitiator according to claims 1 to 7, comprising the stage of:
a) interaction is not necessarily replaced by thioxanthone, and thioxanthone contains at least one hydroxy-group, with a compound selected from the group consisting of epichlorohydrin and esters halogenases acid,
b) interaction of the intermediate obtained in stage a) with the corresponding link in the main chain containing the functional group capable of reaction with the specified intermediate stage (a), or alternative first interaction of the intermediate obtained in stage a)with a compound containing a functional group capable of implementing the function with the specified intermediate stage a), and then the interaction of the thus obtained intermediate with the appropriate link in the main chain;
c) optionally obtaining the derivatives of the compound obtained in stage b).

9. The composition of the coating, preferably printing ink, comprising a polymerised component and at least one photoinitiator according to claims 1-7.

10. The use of photoinitiator according to claims 1 to 7 for curing the coating composition, preferably printing ink.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to a layered material coated with printing paint or printing lacquer. The printing paint or printing lacquer contains as binder at least one non-radiation cured aromatic polycarbonate based on geminally disubstituted dihydroxydiphenyl cycloalkane and as binder solvent at least one radiation cured monomer selected from a group comprising acrylates, methacrylates, vinyl ethers and nitrogen-containing compounds with an ethylene double bond. Said binder is dissolved in the solvent. After curing, the solvent remains in the printing ink or printing lacquer in a chemically cross-linked state.

EFFECT: invention provides high adhesion of the printing ink or printing lacquer to a base, prevents drying thereof on template glass during printing, the need for dilution thereof with a solvent and the undesirable washing off of paint from the print during pressure moulding.

16 cl, 11 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to use of a composition which contains: a) 0.1-20 wt % binder which contains a polycarbonate derivative based on geminally disubstituted dihydroxydiphenyl cycloalkane, b) 30-99.9 wt % solvent, c) 0-10 wt %, with respect to dry mass, dye or mixture of dyes, d) 0-10 wt % functional material or mixture of functional materials, e) 0-30 wt % additives and/or auxiliary substances or a mixture thereof, as jet printing ink. The invention also relates to a method of producing a composite and a composite which contains a polymer layer on which there is a jet printing layer of said composition.

EFFECT: invention is aimed at producing agents which enable to use jet printing in making counterfeit protected documents and/or valuable documents based on polycarbonate layers, and which enable to deposit jet printing layers on layers which meet all optical requirements, which can be coloured, wherein lamination does not deteriorate optical properties of the layers and said layers do not act as a separating layer and facilitate formation of a monolithic composite.

31 cl, 2 tbl, 2 dwg, 8 ex

FIELD: chemistry.

SUBSTANCE: printed paint composition contains aliphatic acid-modified polyester (A) with an attached polybasic acid. The polyester (A) has degree of modification of 35-65 wt %, hydroxyl number of 60-200 mg KOH/g, acid number of 10-60 mg KHO/g and weight-average molecular weight with respect to styrene of 3000-30000, a pigment component and a solvent. Also disclosed is a method of coating a seamless can with said paint composition.

EFFECT: paint composition has high stability, compatibility with coating varnish and high adhesion to the surface of a seamless can while providing good characteristics of coating film.

5 cl, 5 tbl, 20 ex

FIELD: chemistry.

SUBSTANCE: invention relates to organometallic latent catalytic compounds which are suitable as catalysts in polyaddition or polycondensation reactions which are catalysed by a Lewis acid type catalyst, particularly for cross-linking a blocked or non-blocked isocyanate or an isothiocyanate component with a polyol or a polythiol to form polyurethane. Polyaddition or polycondensation reactions are initiated by that a catalyst is released while holding in electromagnetic radiation in wavelength range of 200-800 nm. The latent catalytic compound has formula I or II, Me(FG)(m-x)Ax (I); Ax(FG)(m-1-x)Me-O-Me(FG)(m-1-x)Ax (II), where Me is Sn, Bi, Al, Zr or Ti; m is an integer from 1 to the coordination number of Me; x is an integer from 0 to (m-1); A is a C1-C20 alkyl, halogen, C7-C30 aralkyl, C1-C20 alkoxy group, C2-C10 alkanoyloxy group, C6-C18 aryl or C6-C18 aryl, which is substituted with one or more C1-C20 alkyls; and under the condition that if x is greater than 1, A are identical or different; and FG independently represents a group of formula (Z), (B), (C), (D), (E), (F), (G), (L) or (M)

,

where values of radicals are given in the claim. The invention also relates to a polymerisable composition and a method for polymerisation in the presence of said catalytic compounds. The invention enables to initiate the reaction only if desired by external activation, such as heating or light.

EFFECT: widening the operating window with a polymer mixture until the chain reaction begins.

12 cl, 14 tbl, 67 ex

FIELD: chemistry.

SUBSTANCE: invention relates to polyamide-based printed films which are used as casings for food products, particularly artificial sausage casing. Disclosed is a printing ink system for printing on (co)polyamide-based films. Said system contains a radically curable primer ink and UV radiation radically curable printing ink which forms an almost colourless layer of primer ink. The primer ink contains a reactive compound which, in one molecule, contains a group capable of bonding with a (co)polyamide surface and an ethylenically unsaturated group which can undergo radical-initiated polyaddition. The invention also discloses a (co)polyamide-based single- or multilayer film which is printed with said printing ink system and a method for production thereof.

EFFECT: printing ink system enables to print on (co)polyamide-based food films with high adhesion to the film, resistance to friction, scratching even without an additional lacquer coat, mechanical and thermal processing, resistance to migration of ink components, which prevents foreign odours from food products.

27 cl, 1 ex

FIELD: printing.

SUBSTANCE: carrier based on high-density polymer is decorated with ink for printing, comprising at least one pigment and one binder. The binder is an oxygenised polyolefin wax in the form of an aqueous emulsion, and the wax has a Brookfield viscosity of less than 5000 mPa*s at 150°C and a pH level of 28 to 32 mg KOH/g, and the said ink has a viscosity of less than 2000 mPa*s at 25°C. The ink is applied in a continuous or discrete manner on at least one surface of the carrier. The subject of the invention is also a decorated carrier based on high-density polymer, a multi-layered product, and a method of manufacturing of a multi-layered product with a coating of the said ink.

EFFECT: creation of the ink of simpler composition and easier to use.

16 cl, 1 dwg, 4 tbl

FIELD: textiles and paper.

SUBSTANCE: non-woven fabric is proposed, on the visible surface of which the ink composition is applied comprising from about 40 wt % to about 80 wt % of the dry weight of the ink of linking agent - aziridine oligomer with at least two aziridine functional groups. Also an absorbing article is proposed comprising a liquid-permeable upper layer, an absorbing core and a liquid-impermeable lower layer that contains the specified non-woven fabric with the said applied ink composition. The application of ink on the non-woven fabric can be carried out by the method of flexography or a method of ink-jet printing.

EFFECT: printed non-woven fabric has high resistance to abrasion even in case of its contacting with fatty substance.

16 cl, 2 dwg, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: water based flexographic contains biodegradable polyhydroxyalkanoate (PHA) consisting of monomers having the following formula: where n is an integer from 1 to 5, and R1 is selected from a group comprising hydrogen, alkyl from C1 to C20, and alkenyl from C1 to C20, and having molecular weight ranging from 500 to 5000000 g/mol, binder substance which is three-block amphiphilic compound having two hydrophobic terminal areas with linear and/or branched aliphatic chains CnH2n+2, n = 1-40, and one central hydrophilic area - polyethylene glycol and its derivatives; or having one central hydrophobic area with linear and/or branched aliphatic chains CnH2n+2, n = 1-40, and two hydrophilic terminal areas, a solvent, and a dye or pigment in amount sufficient for leaving a visible mark on a base. Concentration of PHA in the ink ranges from 20 to 80% (weight/volume), concentration of the binder ranges from 0.5 to 20% (weight/volume), concentration of the solvent ranges from 1 to 25% (weight/volume) and concentration of the dye or pigment ranges from 1 to 40% (weight/volume). Described also is a method of preparing water based flexographic ink and a printing composition which contains the said flexographic ink.

EFFECT: improved biodecomposition properties.

13 cl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention pertains to polyurethane resin, which is a product of a reaction between at least one diisocyanate and components, containing functional groups, which have capacity to react with isocyanates, with the following composition: (a) first group, which is formed by one or more polyester-polyols based on ethers, each of which has average molecular mass ranging from 400 to 12000 g/mol, (b) second group, formed by one or more poly hydroxilated resins, chosen from a defined group of resins, (c) optional third group, formed by one or more polyols, each of which has average molecular mass, equal to or less than 800 g/mol, which are also chosen from a defined group of polyols, and (d) at least one amine and a reaction chain-stopping agent. The ratio of equivalent masses of diisocyanate and components, containing functional groups, with capacity to react with isocyanates, is chosen such that, naturally all isocyanate groups of diisocyanate are present as a product of the reaction with one of the above mentioned functional groups, with capacity to react with isocyanates. The invention also relates to the method of obtaining the above mentioned polyurethane resin, to polyurethane resin obtained through such methods, to coating for plastic substrates, containing the proposed resin, as a polyolefin binding substance, to use of such a polyurethane resin as a film forming substance in printing ink for printing on plastic substrates, as well as to the method of obtaining a laminate, which has a layer obtained when printing an image, including stages (a)-(d), with use of coating from polyurethane resin, and to a laminate, obtained using such a method.

EFFECT: obtaining a coating from polyurethane resin, with good heat resistance and excellent initial adhesiveness.

20 cl

FIELD: light industry; composition of decorative coats for wallpaper; manufacture of pearly ink for intaglio printing on wallpaper.

SUBSTANCE: composition of proposed printing ink for wallpaper contains 16-16.5 mass-% of pearly pigment; 12-12.5 mass-% of ethyl alcohol; 46-46.4 mass-% of binder - acrylic latex of butyl acrylate copolymer (19-21%) and methacrylic acid (10-12%) and water; copolymer acrylic latex is produced by method of radiation emulsion polymerization of butyl acrylate, vinyl acetate and methacrylic acid under action of ionizing radiation at dose rate of 0.05-0.1 g/s to absorbed doses of 1.5-2 kgr.

EFFECT: avoidance of lamination of ink; easily washable ink; enhanced heat resistance of ink.

1 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of making heat stabilisers for chlorine-containing hydrocarbons, specifically to a method of obtaining stearates of bivalent metals used in polymer compositions based on chlorine-containing polymers such as polyvinyl chloride, vinylchloride copolymers, chlorinated polyvinylchloride etc. The method of producing heat stabilisers of chlorine-containing hydrocarbons involves reacting stearic acid and oxides or hydroxides of calcium, zinc, barium, magnesium or lead in form of separate of mixed salts of stearic acid in a solid phase with intense stirring. The process is carried out in the presence of sodium hydroxide or potassium hydroxide in amount of 0.05-0.15% of the mass of stearic acid and propylene carbonate or dimethylformamide, or hexamethapol or sulfolane or dimethylsulfoxide in amount of 0.005-0.05% of the mass of stearic acid at 40-95°C in a double-screw reactor. Catalysts of the process - sodium hydroxide or potassium hydroxide and propylene carbonate, or dimethylformamide, hexamethapol, sulfolane or dimethylsulfoxide facilitate considerable increase in activity of the surface of the substrate and, as a result, increase in the rate of the process and obtaining products in form of a homogeneous highly dispersed powder and prevention of secondary oligomerisation of the end product.

EFFECT: use of the invention enables design of a continuous highly efficient method of producing heat stabilisers of chlorine-containing polymers with high heat stabilising capacity due to formation of products in form a homogeneous highly dispersed powder.

2 cl, 4 tbl, 15 ex

The invention relates to the field of medicine and more specifically to ophthalmology, and is intended for the manufacture of intraocular implants, in particular IOLs and contact lenses

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention refers to a compound of formula

,

wherein: each of R1, R2, R4, R5, R6, R7, R8 R9, R10, R11, R12, R13, R14, R15 R16 and R17 is independently specified in a group consisting of deuterium or hydrogen; and R3 is independently specified in a group consisting of CD3 and CH3; provided R3 represents CH3, at least one of the groups R1, R2, R4, R5, R6, R7, R8 R9, R10, R11, R12, R13, R14, R15 R16 and R17 represents deuterium; and R18 represents hydrogen. The invention also refers to a drug on the basis of the above compound for treating a condition causing pain.

EFFECT: there are prepared new compounds inhibiting MMPs (metalloproteinases) which show the high activity, metabolic stability and/or lower toxicity in relation to the currently known MMP inhibitors for treating pain and other diseases, such as cancer.

16 cl, 2 dwg, 14 tbl, 136 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention refers to 6-substituted isoquinoline and isoquinolinone derivatives of formula or to its stereoisomer and/or tautomer forms and/or a pharmaceutically acceptable salt, wherein R1 represents H, OH or NH2; R3 represents H; R4 represents H, a halogen atom, CN or (C1-C6)alkylene-(C6-C10)aryl; R5 represents H, a halogen atom, (C1-C6)alkyl; R7 represents H, a halogen atom, (C1-C6)alkyl, O-(C1-C6)alkyl; R8 represents H; R9 and R6 are absent; R10 represents (C1-C6)alkyl, (C1-C8)heteroalkyl, (C3-C8)cycloalkyl, (C6)hetrocycloalkyl, (C1-C6)alkylene-(C3-C8)cycloalkyl, (C1-C6)alkylene-(C6-C10)aryl, (C1-C6)alkylene-(C6)heterocycloalkyl; R11 represents H; R12 represents (C1-C6)alkyl, (C3-C8)cycloalkyl, (C5)heteroaryl or (C6-C10)aryl; R13 and R14 independently represent H, (C1-C6)alkyl, (C1-C6)alkylene-R'; n is equal to 0; m is equal to 2 or 3; s is equal to 1 or 2; r is equal to 1; L represents O or NH; R' represents (C3-C8)cycloalkyl, (C6-C10)aryl; wherein in the rests, R10, R12-R14 alkyl or alkylene are unsubstituted or optionally substituted by one or more OCH3; wherein in the rests, R10, R12-R14 alkyl or alkylene are unsubstituted or optionally substituted by one or more halogen atoms; wherein (C1-C8)heteroaryl group means (C1-C8)alkyl groups, wherein at least one carbon atom is substituted by O;. (C6)heterocycloalkyl group means a monocyclic carbon ring system containing 6 ring atoms wherein one carbon atom can be substituted by 1 oxygen atom or 1 sulphur atom which can be optionally oxidated; (C5)heteroaryl means a monoring system wherein one or more carbon atoms can be substituted by 1 nitrogen atom or 1 sulphur atom or a combination of various heteroatoms. Also, the invention refers to using the compound of formula (I) and to a therapeutic agent based on the compound of formula (I).

EFFECT: there are prepared new compounds effective for treating and/or preventing diseases associated with Rho-kinase and/or mediated by Rho-kinase by phosphorylation of myosin light chain phosphatase, and the compositions containing these compounds.

32 cl, 111 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention relates to compound of formula or to its therapeutically acceptable salt, where A1 represents N or C(A2); A2 represents H; B1 represents H, OR1 or NHR1; D1 represents H; E1 represents H; Y1 represents CN, NO2, F, Cl, Br, I, R17 or SO2R17; R1 represents R4 or R5; Z1 represents R26 or R27; Z2 represents R30; Z1A and Z2A both are absent; L1 represents R37; R26 represents phenylene; R27 represents indolyl; R30 represents piperasinyl; R37 represents R37A; R37A represents C2-C4 alkylene; Z3 represents R38, R39 or R40; R38 represents phenyl; R39 represents benzodioxilyl; R40 represents C4-C7cycloalkenyl, heterocycloalkyl, which represents monocyclic six- or seven-member ring, containing one heteroatom, selected from O, and zero of double bonds, or azaspiro[5.5]undec-8-ene; the remaining values of radicals are given in i.1 of invention formula. Invention also relates to pharmaceutical composition, based on claimed compound.

EFFECT: novel compounds, which can be applied in medicine for treatment of diseases, in the process of which anti-apoptotic Bcl-2 protein is expressed, are obtained.

8 cl, 2 tbl, 411 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: compounds can find application for preventing or treating cancer, lung cancer, non-small cells lung cancer, small-cell lung cancer, EML4-ALK hybrid polynucleotide-positive cancer, EML4-ALK hybrid polynucleotide-positive lung cancer or EML4-ALK hybrid polynucleotide-positive non-small cells lung cancer. In formula (I) -X-: group of formula , A represents chlorine, ethyl or isopropyl; R1 represents phenyl wherein carbon in the 4th position is substituted by the group -W-Y-Z, and carbon in the 3rd position can be substituted by a group specified in a group consisting of halogen, R00 and -O-R00; R00: lower alkyl which can be substituted by one or more halogen atoms; -W-: a bond, piperidine-1,4-diyl or piperazine-1,4-diyl; -Y- represents a bond; Z represents a monovalent 3-10-membered monocyclic non-aromatic heterocyclic ring which contains 1 to 4 heteroatoms specified in a group consisting of nitrogen, oxygen and sulphur, which can be substituted by one or more substitutes R00; R2 represents (i) an optionally bridged saturated C3-10cycloalkyl which can be substituted by one or more groups specified in -N(lower alkyl)2, lower alkyl, -COO-lower alkyl, -OH, -COOH, -CONH-RZB and morpholinyl, or (ii) a monovalent 3-10-membered monocyclic non-aromatic heterocyclic ring which contains 1 to 4 heteroatoms specified in a group consisting of nitrogen, oxygen and sulphur, which can be substituted by one or more groups specified in a group consisting of lower alkyl, -CO-lower alkyl, oxo, -CO-RZB and benzene; and RZB: phenyl which can be substituted by a group consisting of halogen and -O-lower alkyl; R3 represents -H.

EFFECT: invention refers to new compounds of formula or their pharmaceutically acceptable salts possessing the properties of a selective inhibitor of EML4-ALK hybrid protein kinase activity.

16 cl, 201 tbl, 582 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention relates to methods of treating or relieving severity of disease in patient, where disease is selected from mucoviscidosis, hereditary emphysema, chronic obstructive pulmonary disease (COPD), "dry eye" disease. Methods include introduction of effective amount of N-(5-hydroxy-2,4-di-tert-butylphenyl)-4-oxo-1H-quinoline-3-carboxamide or pharmaceutical composition, containing said compound, to patient.

EFFECT: treatment of relief of disease severity in patient, where disease is selected from mucoviscidosis, hereditary emphysema, chronic obstructive pulmonary disease (COPD), "dry eye" disease.

16 cl, 15 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to novel fungicidally active 5-fluoropyrimidines of general formula I. In compounds of formula , R1 is -N(R3)R4; R2 is -OR21; R3 is: H; C1-C6-alkyl, optionally substituted with 1-3 groups R5; C2-C6-alkenyl, optionally substituted with 1-3 groups R5; a 5- or 6-member heteroaromatic cycle, selected from a group consisting of furanyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, thiazolyl, thiadiazolyl, oxazolyl, isoxazolyl, triazolyl; wherein each heteroaromatic cycle is optionally substituted with 1-3 R29 groups; 3H-isobenzofuran-1-oyl; -C(=O)R6; -C(=S)R6; -C(=S)NHR8; -(=O)N(R8)R10; -OR7; -P(O)(OR15)2; -S(O)2R8;-SR8; -Si(R8)3; -N(R9)R10; -(CHR24)mOR29 or -C(=NR16)SR16; where m equals an integer from 1 to 3; R4 is: H; C1-C6-alkyl, optionally substituted with 1-3 R5 groups; or -C(=O)R6; alternatively, R3 and R4 together can form: a 5- or 6-member saturated or unsaturated cycle containing 1-2 heteroatoms selected from N and O, where each cycle can be optionally substituted with 1-3 R11 groups; =C(R12)N(R13)R14 or =C(R15)OR15. The rest of the radicals are given in the claim.

EFFECT: obtaining novel fungicidally active 5-fluoropyrimidines of general formula I.

4 cl, 3 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to 5-membered heterocyclic compounds of general formula (I), their prodrugs or pharmaceutically acceptable salts, which possess xanthine oxidase inhibiting activity. In formula (I) T represents nitro, cyano or trifluoromethyl; J represents phenyl or heteroaryl ring, where heteroaryl represents 6-membered aromatic heterocyclic group, which has one heteroatom, selected from nitrogen, or 5-membered aromatic heterocyclic group, which has one heteroatom, selected from oxygen; Q represents carboxy, lower alkoxycarbonyl, carbomoyl or 5-tetrasolyl; X1 and X2 independently represent CR2 or N, on condition that both of X1 and X2 do not simultaneously represent N and, when two R2 are present, these R2 are not obligatorily similar or different from each other; R2 represents hydrogen atom or lower alkyl; Y represents hydrogen atom, hydroxy, amino, halogen atom, perfluoro(lower alkyl), lower alkyl, lower alkoxy, optionally substituted with lower alkoxy; nitro, (lower alkyl)carbonylamino or (lower alkyl) sulfonylamino; R1 represents perfluoro(lower alkyl), -AA, -A-D-L-M or -A-D-E-G-L-M (values AA, A, D, E, G, L, M are given in i.1 of the invention formula).

EFFECT: invention relates to xanthine oxidase inhibitor and pharmaceutical composition, which contain formula (I) compound.

27 cl, 94 tbl, 553 ex

FIELD: chemistry.

SUBSTANCE: invention relates to substituted pyrrolidine-2-carboxamides of formula I or their pharmaceutically acceptable salts, where values X, Y, R1, R2, R3, R3, R4, R5, R6 and R7 are given in item 1 of the formula. Compounds can be used in pharmaceutical composition, inhibiting interaction of MDM2-p53.

EFFECT: compounds can be used as anti-cancer medications.

46 cl, 4 dwg, 347 ex

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