Layered material coated with radiation cured printing paint or printing lacquer and moulded component

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

 

The present invention relates to a layered material, covered with a radiation-curable printing ink or printing varnish, as well as to the method of manufacturing the specified layered material, involving the use of the specified printing varnish, respectively, of the specified ink. In addition, the invention relates to undergo subsequent pouring molded parts containing the specified layered material, and method of manufacturing the specified molded parts.

The prior art printing ink based on the solid resin primarily based polycarbonates, which in typical cases is dissolved in a halogen-free solvents. The printing ink of this type is shown, for example, in the claims of the European patent EP 0688839 B1 described in which the polycarbonate should be considered as a possible binder for one of the embodiments of the present invention.

The disadvantage of the prior art of printing inks is that in case of presence of solvents, they are prone to due to volatilization of the solvent drying on the mesh screen forms that primarily refers to the periods of production downtime (no printing). This results in within the of screen mesh, requiring additional purification. In the worst case, the stencil form becomes unsuitable for further use. Another disadvantage of the prior art printing technology is that the drying of printing ink should be warm air in the drying duct or furnace, which leads to an increase in the duration of the technological process, and therefore, no possibility of optimization. In addition, thermal drying infrared drying requires additional manufacturing space and additional energy consumption, and hence increase costs.

In addition, the prior art radiation-curable resin containing reactive, including UV-curable monomers. In the corresponding patent application great Britain GB 2370279 As described radiation curing of polyurea-nakilat with polycarbonate structural component, however, the drawback of such a polymer is poor suitability for processing. In the implementation process of the so-called subsequent injection molding, whereby the sealed ink side of the polycarbonate film by casting under pressure is applied an extra layer of thermoplastic polymer is, arises the problem of low adhesion, which primarily relates to printing on polycarbonate substrate. By such subsequent molding in principle, it is possible to produce materials type of sandwich, the paint layer which is located between the polycarbonate film and a layer deposited by a subsequent injection molding of the polymer, thus avoiding abrasion of the print everyday use such material. Another disadvantage of the technologies of the prior art is observed in the process of forming the adhesion of the print to the form, as well as increased sensitivity of the fingerprint to pressure and temperature, which is undesirable leaching of the dye in the subsequent injection molding, and therefore, deterioration of printing quality.

With regard to the foregoing, the present invention was based on the task to offer a layered material, respectively, a method of manufacturing a layered material with printing ink and printing ink and/or printing varnish should have a higher and better adhesion to the substrate. When this first was to eliminate the need to use of volatile solvents, and therefore, undesirable drying of the printing ink on the mesh screen forms in the printing process, and also to eliminate h is the need for additional dilution of the ink solvent and thereby reduce the duration of the process. This makes it possible to obtain prints with finer details, and consequently, to improve the print quality. In addition, it is possible to avoid undesirable leaching of the ink from the print and deterioration of its quality, while the implementation of additional technological operations subsequent injection molding.

The specified task according to the invention is solved with the help of layered material that includes:

a) polozka at least one thermoplastic polymer, preferably a film of at least one thermoplastic polymer,

b) single-layer or multilayer colorful and/or lacquer film of printing ink or printing varnish containing:

as a binder at least one non-radiative curing aromatic polycarbonate based on gemenele disubstituted dihydroxydiphenylsulfone as solvent at least one radiation curable monomer selected from the group comprising acrylates, methacrylates, simple vinyl esters and nitrogen-containing compounds with ethylene double bond,

characterized in that the binder dissolved in the solvent, after which curing remains in the printing ink or printing varnish in chemically cross-linked state.

The preferred improved variants are given in the dependent PU is the settlement of the claims.

According to the invention in an unexpected circumstance first of all is the opportunity of education is predominantly stable solution of thermoplastic polycarbonate in a variety of radiation curable monomers suitable for subsequent formation of a film by UV curing in the presence of a thermoplastic polycarbonate. Such an opportunity according to the invention is used, to a subsequent screen printing to ensure the absence of drying printing inks and/or print varnishes based on a specified solution on the grid, eliminating the need for additional dilution and/or due to their drying needs to be cleaned stencil shapes, as well as to exclude other costs. In typical cases (approval of liquid printing inks and/or print varnishes preferably carried out under the action of UV radiation, light emitting diodes or, if necessary, used electron beam, resulting in exceptionally high speed of the corresponding process, which typically occurs during the period of time, much less a second. After curing, the prints are subjected directly to further processing without the prior transmission, for example, through a drying channel implemented with a view the completion of the supply of additional heat. This significantly reduces the duration of processing fingerprints and increases the overall performance of the process. Another favourable circumstance is that by preventing the leaching of paint and other unwanted effects in combination with a higher adhesion to the film substrate can be obtained prints with fine details, which opens the possibility of using the technology of screen printing in other areas.

In accordance with the invention, the definition of "UV (stitched)", "radiation-curable (stitched)", used to refer to the fact that the cured ink film is carried out by radical chain polymerization. The difference between ordinary solvents of the prior art and used in accordance with the present invention curable monomer, which acts as the solvent medium for polycarbonate, is that normal solvent in the drying of the paint evaporates into the environment, while curing the monomer remains in the ink film. This makes it possible to eliminate the possibility of harmful effects of volatile organic compounds on the environment during the drying-based solvent systems. However, much more to nachna installation for UV curing requires the printshop much less additional manufacturing space. Another advantage of UV curing is less energy compared to the energy consumption for heating the drying channel in the case of drying based solvent systems.

In accordance with the invention, the definition of "non-radiative curing" used primarily in order to ascertain the absence of in-curable compound reactive double bonds.

Radiation-curing printing inks, like any other printing inks and/or print varnishes in addition to used according to the invention the binder can contain many other components and, obviously, should be brought in line with their intended purpose and character is to be printed substrate. To other components of printing inks include, for example, pigments, fillers and auxiliary means, which in most cases need only be used in extremely small amounts, however, should be aware that their use often allows to solve some technological problems.

In this preferred feature poterjannogo under the action of UV radiation thermoplastic polycarbonate, used in combination with the monomer, which in typical cases is non-volatile compound (or at least has a slight volatile the stew), is to ensure strong adhesion of the paint layer with the substrate (for example, a polymer substrate), and therefore, the stability of the finished prints to abrasion, heat and mechanical bending, and their stability under the conditions normally used for subsequent fill sealed film molding. In the absence of volatility of the individual components of printing ink there is also no need for additional process steps, in particular, performed in the printing process the additional dilution, which according to the prior art it is necessary, for example, in the case of halogen-free solvents.

In addition, used according to the invention, the polycarbonates preferably have high heat resistance, and extremely high flexibility, and therefore they are ideally suitable for processing by injection molding and other methods.

For the practical implementation of the present invention is particularly suitable known from the above European patent EP 0688839 B1 polycarbonates Bayer MaterialScience AG, however, in accordance with the present invention such polycarbonates in contrast to the prior art used in the form of solutions in UV-curable or radiation-curable monomial is re or a mixture of curable monomers.

According to the invention colorful film may be a single layer or a multilayer. In the case of multi-layer paint film on each other can be applied several identical or different paint layers. According to the invention may be preferred multilayer colorful film.

Another object of the present invention is the manufacturing method proposed in the invention of layered material, wherein the substrate, the first film of thermoplastic polymer, method of printing, especially by screen printing, provided with a coating in the form of ink film and/or varnish film, which is subjected to subsequent radiation curing.

In a preferred embodiment of the proposed invention in the method of forming it is possible to expose the substrate before application of a colorful and/or a lacquer layer or a laminated material after application to the substrate colorful and/or a lacquer layer.

In the case of forming the layered material after application to the substrate colorful and/or a lacquer layer obtained by forming a laminate unexpectedly characterized by the absence of cracking in the ink film and the adhesion ink film used for forming the tool.

The total thickness of the proposed invention is ostogo material, includes a substrate and a colorful or lacquer film, is preferably in the range from 0.05 to 4 mm, particularly preferably from 0.1 to 2 mm, even more preferably from 0.2 to 2 mm, the overall thickness of the specified layered material according to the invention can reach 20 mm, preferably 19 mm

Preferred method of manufacturing the layered material (below called molded part according to the invention is that the sealed offer in the invention of the printing ink towards the substrate (proposed in the invention of layered material) is poured (thermoplastic) polymer using, for example, this technology subsequent injection molding. This technology will enable the production of products with optimally protected from abrasion of the printed pattern.

Thus, an object of the present invention is also moulded with subsequent filling, characterized in that the sealed printing ink or printing varnish party proposed in the invention laminates subjected to single or multiple filling at least one thermoplastic polymer, and the temperature used for the subsequent casting of thermoplastic polymer is 200°C or higher.

With the invention of the layered material the ial group may be subjected to subsequent fill one or more layers, consisting of at least one thermoplastic polymer.

Other examples of disclosure of such molded parts and related products, primarily otnosjawiesja to the layered structure, the substrate, and another thermoplastic polymer, indicated in the European patent EP 0691201 B1 and are not limited herein data.

So, for example, proposed in the present invention molded parts, examples of which are described in European patent EP 0691201 B1, can consist of the following structural elements (but are not limited to):

1. single-layer or multilayer film of thermoplastic polymer, the preferred thickness of from 0.02 to 0.8 mm,

2. single-layer or multi-layer paint film is preferred thickness of from 3 to 50 mm,

3. optionally, at least one non-adhesive at room temperature polyurethane layer and

4. performed by subsequent fill the layer of thermoplastic polymer, the preferred thickness of from 0.1 to 19 mm, which, in turn, consists of one or more polymer layers.

When this layer of thermoplastic polymer (4) can be applied to layers (1+2), respectively (1+2+3), performed by known methods further casting (see, for example, German patent application DE-OS 27 55 88).

Such molded parts consisting of layers (1+2+4) and optionally a layer (3), can be produced, for example, the fact that films of thermoplastic polymers by the method of screen printing is applied at least one paint layer and optionally at least one polyurethane layer, and after or before applying the polyurethane layer carry out the molding material, and concludes with known methods then fill with a layer of thermoplastic polymer. Combined film materials with polyurethane bonding in principle known (see, for example, German patent application DE-OS 25 17 032 and DE-AS 30 10 143). In addition, known then fill thermoplastic polymer films of thermoplastic polymers, the method performs the subsequent molding (see German patent application DE-OS 27 55 088), as well as the subsequent injection molding of thermoplastic films with an intermediate colored layer (see German patent application DE-OS 35 28 812).

Substrate and thermoplastic polymers suitable for the manufacture of such molded parts, known in the art and are described in European patent EP 0691201 B1.

A significant advantage of the present invention is that through the use of printing ink in the form dissolved in the UV-curable monomers, polycarb the ATA, which can be subjected to simple radiation curing, preferably UV-curing, can provide a higher adhesion of the paint layer to the sealed substrate, formability provided with a colored layer of the substrate without damaging the paint layer, and then filling accompanied with colorful substrate layer of a thermoplastic polymer without leaching or destruction of the paint film.

The glass transition temperature of the paint, especially the glass transition temperature of the polycarbonate contained in the paint as a binder, can be both below and above the glass transition temperature of the substrate.

However, favorable can also be used as a binder of polycarbonate, glass transition temperature than the glass transition temperature of the substrate. The glass transition temperature of the respective polymers are determined according to ISO 11357.

According to the invention the manufacture of molded parts, followed by pouring carried out by single or multiple fill sealed printing ink or printing varnish parties proposed in the invention of layered material at least one thermoplastic polymer at a temperature of 200°C or higher.

With subsequent filling can be accomplished, for example, by injection molding, molding or foaming, etc is doctitle by injection molding. Appropriate technology further casting in principle known in the art and described in the literature (see, for example, German patent application DE-OS 27 55 088 or public technical information 7010 ATI and ATI 7007 Bayer MaterialScience AG (formerly Bayer AG)published, for example, in the magazine "Kunststoffe", 9/99.

In an even more preferred embodiment, the sealed printing ink or printing varnish direction proposed in the invention of the laminate by the method of printing, especially screen printing, put a layer of polyurethane, and then perform the fill material at least one thermoplastic polymer.

Other advantages, features and details of the present invention, including structural formulas, recipes, methods and parameters given in the following description. In accordance with the invention can be used in any combination. In order to avoid repetition of the inventive distinctive signs belonging to the substances, also belong to the claimed method. And, on the contrary, related to the way the claimed distinguishing characteristics are also related to the claimed substances.

Under the methods of printing in accordance with the present invention involve, for example, screen printing, rotary screen printing, pad printing, offset printing, flexographic the printing, gravure printing or ink jet printing. According to the invention, it is preferable to screen printing.

Curing printing inks preferably performed by means of UV radiation with a wavelength range from 200 nm to 450 nm, sufficient to ensure full curing of the printing ink or printing varnish. In accordance with another variant of the printing ink or printing varnish can be cured by means of electron flow without the use of photoinitiators. Thus, if used in the following description, the definition of "UV" refers to the fact that the curing can be performed also by used as alternatives to other radiation, such as electron flow. In addition, for drying UV ink, you can use the led devices that emit nearly monochromatic light in the ultraviolet range or close range.

Printing can be performed, providing the whole range of color tones. In the case of the method of screen printing is the preferred use of the subject fabric for screen forms with parameters from 100-40 to 180-27, preferably 140-34 or 150-31, which corresponds to the thickness of the paint layer 5-12/μm. Depending on the purpose of printing and the type of printing machine curing implemented Aut through predominantly focused market mercury lamps, medium-pressure or lamps with doped mercury, the specific capacity ranges from 80 to 400 W/cm, preferably from 120 to 200 W/see Duration of exposure depends on the speed of printing, since the printing device and exposimeters are connected to each other. When the sealing film materials, the speed of printing is usually from 1 to 50 prints per minute.

For abrasion resistant decoration of molded products to be performed, for example, by subsequent injection molding, it is necessary to use a binder which does not melt at high temperature injection molding, however, firmly desirous to the substrate and have the flexibility. These requirements satisfy special polycarbonates with high heat resistance.

In this regard, the use of flexible printing inks or varnishes preferably with high heat resistance, which contain:

A) as a binder at least one non-radiative-veryday aromatic polycarbonate based on gemenele disubstituted of dihydroxydiphenylsulfone, and

B) as solvent at least one radiation curable monomer selected from the group comprising acrylates, methacrylates, simple vinyl esters and nitrogen-containing compounds with ethylene double bond, characterized in that the binder dissolved in the solvent, after which the CTE is confirm remains in the printing ink or printing varnish in chemically cross-linked state.

To fit the polycarbonates are preferably high molecular weight, thermoplastic aromatic polycarbonates with srednevekovoi molecular weight (Mw) of at least 10000, preferably from 20,000 to 300,000, which contain bifunctional carbonate structural units of the formula (I):

in which

R1and R2independently from each other, respectively, denote hydrogen, halogen, preferably chlorine or bromine, alkyl with 1-8 carbon atoms, cycloalkyl with 5-6 carbon atoms, aryl with 6-10 carbon atoms, preferably phenyl, or aralkyl with 7-12 carbon atoms, preferably phenylalkyl with 1-4 carbon atoms in the alkyl, especially benzyl,

m means an integer from 4 to 7, preferably 4 or 5,

R3and R4independently from each other, respectively, denote hydrogen or alkyl with 1-6 carbon atoms, chosen individually for each X, and

X mean carbon, and

n means an integer of 30 or higher, especially preferably from 50 to 900, more preferably from 60 to 250,

provided that the residues R3and R4attached to at least one atom X, simultaneously denote alkyl.

Initial products to obtain polycarbonates are di-hydroxydiphenylamine formula (Ia):

1, R2, R3, R4, m and n are such as defined for formula (I).

Attached to the atoms of X residues R3and R4simultaneously denote alkyl, preferably for one and two atoms X, primarily made up of only one atom X.

Preferred alkyl residue is methyl; the atoms X, in the alpha position relative to diphenylsilane the carbon atom (C-1), preferably are not dialkylammonium, while the atoms X, in the beta position relative to C-1, are preferably dialkylammonium.

Preferred are dihydroxydiphenylsulfone with five or six ring carbon atoms in the cycloaliphatic residue (t in the formula (Ia) means 4 or 5), for example, divinely formula (Ib)to(Id);

,

,

,

especially preferred is 1,1-bis(4-hydroxy-phenyl)-3,3,5-trimethylcyclohexane (compound of formula (Ib) with the same residues R1and R2signifying hydrogen). The polycarbonates can be obtained from diphenols formula (la) in accordance with German patent application P 3832396.6, respectively the European patent application EP-A 0359953.

From diphenol formula (Ia) are homopolymerisation, and to obtain copolycarbonates use the form multiple source diphenols formula (Ia).

In addition, to obtain high molecular weight, thermoplastic aromatic polycarbonates can also be used divinely formula (Ia) in a mixture with other diphenolate, for example, diphenolate formula (Ie):

.

Suitable other diphenolate formula (1E) are compounds in which Z denotes an aromatic residue with 6-30 carbon atoms, which may contain one or more aromatic nuclei, may be substituted and may contain as bridge members aliphatic residues, other cycloaliphatic residues, such as in the formula (Ia), or heteroatoms.

Examples of diphenols formula (Ie) are hydroquinone, resorcinol, dihydroxydiphenyl, bis(hydroxyphenyl)alkanes, bis(hydroxy-phenyl)cycloalkanes, bis(hydroxyphenyl)sulfides, bishydroxyethyl ethers, bis(hydroxyphenyl)ketones, bis(hydroxyphenyl)sulfones, bis(hydroxyphenyl)sulfoxidov, α,α'-bis(hydroxyphenyl)diisopropylbenzene, as well as their alkylated and halogenated in the nucleus derived.

The above and other suitable divinely described, for example, in applications U.S. patent US-A 3 028 365, US-A 2 999 835, US-A 3 148 172, US-A 3 275 601, US-A 2 991 273, US-A 3 271 367, US-A 3 062 781, US-A 2 970 131, US-A 2 999 846, German patent applications DE-a 1 570 703, DE-A 2 063 050, DE-A 2 063 052, 2 211 956, application France FR-A 1 561 518, in the monograph by N. Schnell, Chemistry and Physics of Polycarbonates, issued elsto Interscience Publishers, New York, 1964.

Preferred other diphenolate are, for example, 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane, 2,4-bis(4-hydro-xifer)-2-methylbutane, 1,1-bis(4-hydroxyphenyl)cyclohexane, α,α-bis(4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis(3-methyl-4-hydro-xifer)propane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, bis(3,5-dimethyl-4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4-hydroxy-Fe-nil)propane, bis(3,5-dimethyl-4-hydroxyphenyl)sulfon, 2,4-bis-(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, α,α-bis(3,5-dimethyl-4-hydroxyphenyl)-n-diisopropylbenzene, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane and 2,2 bis(3,5-dibromo-4-hydroxyphenyl)propane.

Especially preferred diphenolate formula (Ie) are, for example, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane and 1,1-bis(4-hydroxyphenyl)cyclohexane.

The preferred diphenols formula (Ie) is 2,2-bis(4-hydroxyphenyl)propane. Other divinely can be used separately or as mixtures.

The molar ratio of diphenols formula (Ia) to optionally shared with other diphenols formula (Ie) is in the range from 100:0 to 2:98, preferably in the range from 100:0 to 10:90, especially in the range from 100:0 is about 30:70.

High molecular weight polycarbonates can be obtained from diphenols formula Ia)used optionally in combination with other diphenolate, known methods for the synthesis of polycarbonates. Different divinely can connect to each other as statistically and with the formation of blocks.

Proposed in the invention, the polycarbonates can be branched known methods. Branching polycarbonates can be achieved by a known method involving the use of for polycondensation negligible amounts trifunctional compounds or compounds with higher functionality, primarily compounds with three or more phenolic hydroxyl groups, and the preferred amount of these compounds is from 0.05 to 2.0 mol%. in terms of the initial divinely. Suitable branching agents with three or more phenolic hydroxyl groups are:

phloroglucin, 4,6-dimethyl-2,4,6-three(4-hydroxyphenyl)heptan-2, 4,6-dimethyl-2,4,6-three(4-hydroxyphenyl)heptane, 1,3,5-three(4-hydroxy-phenyl)benzene, 1,1,1-three(4-hydroxyphenyl)ethane, three(4-hydroxyphenyl)-phenylmethane, 2,2-bis[4,4-bis(4-hydroxyphenyl)cyclohexyl]propane, 2,4-bis(4-hydroxyphenylethyl)phenol, 2,6-bis(2-hydroxy-5-methylbenzyl) -4-METHYLPHENOL, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxy-phenyl)propane, hexa esters[4-(4-GI is recipientemail)-phenyl]ochoterenai acid, Tetra(4-hydroxyphenyl)methane, Tetra[4-(4-hydroxyphenylethyl)phenoxy]methane and 1,4-bis[4',4"-dihydroxydiphenyl)methyl]benzene.

To some other trifunctional compounds include 2,4-dihydroxybenzoic acid, tremezzina acid, cyanuric chloride and 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindol.

As agents of breakage of polymer chains that are designed for the well-known regulation of the molecular weight of polycarbonates, use of monofunctional compounds in normal concentrations. Suitable compounds of this type include, for example, phenol, tert-butylphenol or other alkyl substituted phenols. To regulate the molecular weight of the polycarbonates primarily suitable to be used in small amounts of phenols of formula (If):

,

in which

R is a branched alkyl residue with eight and/or nine carbon atoms.

The content of CH3-protons in the alkyl residue R is preferably from 47 to 89%, while the content of CH and CH2-protons is in the range from 53%to 11%, and the remainder R is preferably located in the ortho and/or para-position relative to the hydroxyl group and the upper limit of the content of ortho-faction, especially preferably 20%. Agents breakage of polymer chains is General used in amounts of from 0.5 to 10 mol%, preferably from 1.5 to 8 mol%. in terms of the initial divinely.

The polycarbonates preferably can be obtained by known polycondensation method at the phase boundary (see N. Schnell "Chemistry and Physics of Polycarbonates", Polymer Reviews, volume IX, pp.33 and following, publisher Interscience Publ., 1964).

Thus divinely formula (Ia) is dissolved in an alkaline aqueous phase. To obtain copolycarbonates a mixture of diphenols formula (Ia) with other diphenolate, for example, diphenolate formula (Ie). To regulate the molecular weight can be added agents breakage of polymer chains, for example, the compounds of formula (If). The interaction of diphenols with phosgene is carried out in accordance with the method of polycondensation on the phase boundary in the presence of a solvent preferably polycarbonate inert organic phase. The temperature of the polycondensation is from 0 to 40°C.

If necessary, shared agents branching chains (preferably in quantities of from 0.05 to 2.0 mol%.) you can enter in an alkaline aqueous phase together with diphenolate or add before postironium in the form of a solution in an organic solvent. In addition diphenols formula (Ia) and optionally other diphenols formula (Ie) can share their complex monetary with monochloroamine and/or baharoglu acid, which is added in the form of races the thieves in organic solvents. In this case, the number of agents breakage of the chains, as well as agents of their branching is determined by the molar amount of diphenolate residues in accordance with formula (Ia) and optionally formula (Ie); when sharing esters harpalinae acid can be respectively known way to reduce the number of phosgene.

Organic solvents suitable for dissolving agents break chains, and optionally agents to use branching and esters harpalinae acids are, for example, methylene chloride, chlorobenzene, primarily a mixture of methylene-chloride with chlorobenzene. Used agents break chains and branching agents optionally can be dissolved in the same solvents.

The organic phase for polycondensate on the phase boundary is, for example, methylene chloride, chlorobenzene and mixtures of methylene chloride with chlorobenzene.

As the alkaline aqueous phase is used, for example, caustic soda solution. To obtain polycarbonates can be used conventional polycondensation catalysts on the phase boundary, such as tertiary amines, especially tertiary aliphatic amines, in particular tributylamine or triethylamine, in an amount of from 0.05 to 10 mol%. in terms of the initial divinely. The catalysts can add recipients shall be before or after vosganian.

The polycarbonates can be obtained by a known method in a homogeneous phase (the so-called pyridine method), as well as known method of transesterification in the melt, involving the use of, for example, diphenylcarbonate instead of phosgene.

The polycarbonates preferably have srednevekovoi molecular weight (Mw)determined by gel-chromatography after prior calibration, which is at least 10000, particularly preferably from 20000 to 300000 and above all from 20000 to 80000. The polycarbonates can be both unbranched and branched, as well as homopolymerization and copolycarbonate based diphenols formula (Ia).

By embedding diphenols formula (Ia) formation of new polycarbonates with high heat resistance, which have optimal complex of other properties. This applies primarily to the polycarbonates based diphenols formula (Ia)in which m means 4 or 5, and even more to polycarbonates based diphenols formula (Ib)in which R1and R2independently from each other, respectively, such as described for formula (Ia), and particularly preferably denote hydrogen.

Thus, especially preferred are polycarbonates with structural units of the formula (I)in which m means 4 or 5 more before occhialino with structural units of the formula (Ig):

in which R1, R2and n, respectively, such as described for formula (I), but is particularly preferably denote hydrogen.

Such polycarbonates based diphenols formula (Ib)in which R1and R2first of all, mean hydrogen, in addition to high heat resistance suddenly have a high UV stability and optimal flow in the melt, as well as extremely high solubility in the following monomers.

In addition, the properties of the polycarbonates can have a beneficial impact due to the use of combinations with other diphenolate, primarily diphenolate formula (Ie). The content of structural units diphenols formula (Ia) in a similar copoly-carbonates ranges from 100 to 2 mol%, preferably from 100 to 10 mol%, first of all, from 100 to 30 mol%. in terms of the total number diphenolic structural units (100 mol%).

Particularly preferred polycarbonates are copoly-carbonates of the formula (I-D), in which the structural units of the respective comonomers can be arranged in alternating, block or random sequence, and p+q=n, and q and p are related to each other analogon specified in the previous paragraph, the molar ratio between the structural units of formulas (Ie) and (Ia).

.

With the purpose of obtaining a printing ink or printing varnish used for deposition on a substrate in the form of a colorful or varnish film, polycarbonate is dissolved in one or more UV-curable monomers, the suitability of which the crosslinking is caused, for example, which are suitable for polymerization of acrylate or Ethylenediamine groups. Preferred monomers of this type are monofunctional acrylates. However, as these monomers can also be used defunctionalize, trifunctional or more highly functional acrylates or methacrylates.

Such UV, respectively, of a radiation-curable monomers are used for dissolving polycarbonate, however, unlike the solvents used, for example, in accordance with European patent EP 0688839 B1, they act in accordance with a different principle. The purpose of the common solvents, for example, solvents used in accordance with the above-mentioned patent, is solely the dissolution of the polycarbonate.

Conventional solvents with subsequent drying of the printed ink be the most complete, i.e. almost 100% evaporation, and therefore do not have film-forming properties. In accordance with the present invention, in contrast, uses the t stitched monomers, which should also dissolve the polycarbonate, but they almost completely (in the best case, 100%) remain in the paint and therefore have a significant impact on the properties of the cured paint, as well as on the properties of the resulting paint film. The volatility of radiation-curable monomers should preferably be less than 5%, particularly preferably less than 1%.

According to the invention as stitched monomers can be used, for example, isobornyl(meth)acrylate (IBO(M)A), 2-phenylethyl(meth)acrylate (D(M) (A), ethoxylated 2-phenyl-ethoxyacrylate, methoxylamine poliatilenglikole(meth)acrylates, alkoxycarbonyl tetrahydro-furfuryl(meth)acrylate, alkoxycarbonyl laurelcrest, alkoxycarbonyl phenylacrylate, stearyl(meth)acrylate, lauryl(meth)acrylate, Isodecyl(meth)acrylate, isooctadecyl, octylacrylate, tridecyl(meth)-acrylate, caprolactone, ethoxylated or alkoxysilane-tion Nonylphenol(meth)acrylate, cyclic trimethylolpropane, getidelement, propilenglikolmonostearata, 2-(2-ethoxyethoxy)acrylate (EAEAEA), methyl methacrylate (MMA), propoxycarbonyl alismataceae, the ethoxylated hydroxyethylmethacrylate, ethoxydiglycol-methacrylate, 1,6-hexanediol(meth)acrylate (HDDs(M) (A), alkoxyimino-bath hexaniacinate, alkoxysilane is clohexane-metanode(meth)acrylates, 1,3-butyleneglycol(meth)acrylate, 1,4 butane-cioldi(meth)acrylate, diethyleneglycol(meth)acrylate, polyethylene glycol(200)diacrylate, polyethylene glycol(400)di(meth)acrylate, poly-ethylene glycol(600)di(meth)acrylate, ethoxylated bisphenol a di(meth)acrylates, tetraethyleneglycol(meth)acrylate, triethylene-Kaldi(meth)acrylate, etilenglikolevykh, polyethylene glycol-dimethacrylate, dipropyleneglycol (DPGDA), alkoxycarbonyl neopentylglycol(meth)acrylate, propoxycarbonyl trim-cellproperties trimethylolpropane(meth)acrylate, propoxycarbonyl glyceryltrinitrate (GPTA), dipentaerythritol (DPHA), tripropyleneglycol (TPGDA), dipentaerythritol (DiPEPA), pentaerythrityl (PETIA), (ethoxylated) pentaerythritoltetranitrate, detrimentalist, trimethyl-proventricular (TREAT), tricyclopentadiene (TCDDMDA), dipentaerythritol, low molecular weight monofunctional urethaneacrylate, low-molecular epoxyacrylate or hydroxypropylmethacrylate (NRMA), and the list may be used for stapling monomers is not limited to the above compounds.

Even more preferred stitched the monomers from the above list include 2-phenylethyl(meth)acrylate (D(M) (A), ethoxylated 2-phenylacetoacetate, t is traditionalmedicine, 2-(2-ethoxyethoxy)acrylate (EAEAEA), methyl methacrylate (MMA) and 1,6-hexanediamine (HDDA).

In addition, as the stitching of the monomers, you can use some simple vinyl esters such as vinyl ethers of diethylene glycol (DVE-2) or vinyl ethers of triethylene glycol (DVE-3), and monomers of this type are not ohranychytsya these compounds.

Suitable compounds with Ethylenediamine communication include, for example, N-vinyl pyrrolidone (NVP), N-vinylcaprolactam, N-vinylformamide (NVF) or gilmorton (ASMO) without limiting these compounds. However, the use of N-vinylpyrrolidone (NVP) is known for sanitary reasons should be avoided.

To a binder for printing inks or varnishes in the General case, add one or more additional UV-curable or radiation-curable monomers. Under additional monomers, which are also involved in the curing, mean UV-curable monomers mentioned above for the solution of copolycarbonates. The total number of UV-curable monomers in the range from 1 to 99 wt. -%, preferably from 25 to 85 wt. -%, first of all, from 50 to 85% of the mass.

The process of crosslinking monomers implement, such as UV curing, (approval under the action of LEDs or e is chronologies curing. These are known from the literature methods of curing are used in different spheres of the prior art, for example, for the sealing of optical media.

In accordance with the present invention the technology of radiation curing with its inherent advantages can be combined with the technology of curing in the molds, in particular injection molds.

To the printing ink or printing the lacquer preferably not add volatile organic solvents. However, to optimize the characteristics of the printing ink or printing varnish, designed for use in specific fields, you can add volatile solvent. Because many sold on the market of active substances dissolved in the solvent or diluted with solvents, a small amount of the latter can get into the paint together with appropriate additives. The content of volatile organic solvents in the printing ink or printing varnish should not exceed 10%, preferably 5%. In a particularly preferred embodiment, it should completely abandon the use of volatile organic solvents.

In addition, the printing ink or printing varnish used in addition to the polycarbonate may contain at least one other resin.

Additional resin may be you are the wounds from the group includes a variety of resins. Examples of suitable additional resins are epoxy resins, polyester resins, cellulose resins, copolymers of methyl methacrylate (for example, Paraloid B-48N, Paraloid B60, Paraloid B-82 company Rohm & Haas Deutschland GmbH, Kron 4, D-60489 Frankfurt, Neocryl B-810 company Neoresins Lurgiallee 6-8, D-60439 Frankfurt-on-main); ethyl methacrylate (for example, Paraloid 72 company Rohm & Haas); copolymers of butyl methacrylate (for example, Dega-lan LP 65/12, innovations for this LP 68/04 company Rohm GmbH & Co KG, Kirschenal-lee); liquid epoxy resin (for example, Polypox E 064 company UPPC AG, Schemmerbergerstr. 39, D-88487 Metingen, resin RQtapox 0164 firm Bakelite AG, Araldit GY 250 firm Vantico); unsaturated polyester resins (for example, adhesive resin LTH firm Degussa Chemiepark Mari, Paul-Baumann-Str. 1, 45764 Mari); saturated polyester resin (Dynapol L 912, Dynapol L 952 company Degussa), and the above list is not limited to the designated representatives. Such additional resin can be used to optimize certain characteristics, such as adhesion, in the amount of from 0 to 50 wt. -%, preferably from 0 to 20 wt. -%, particularly preferably from 0 to 5% of the mass. dry weight calculated on the total weight of the paint or varnish. However, when the added amount of said additional passive or inert resins that are chemically different from that used as the base resin of polycarbonate, note that they both rights is lo increase the risk of leaching of the dye in the subsequent injection molding.

Printing inks or varnishes preferably contain at least one photoinitiator, usually two, three or more photoinitiator intended to initiate the superficial and deep curing (crosslinking) of the paint layer under the action of UV radiation. Preferred are photoinitiator with minimal propensity to migrate and minimum volatility, in order to avoid negative effects, such as peeling paint from injection molded products. In addition, used photoinitiator must have a minimum tendency to yellowing, in order to exclude the change or distortion of the color components.

Photoinitiator can be selected from the group including commonly used in UV-curing printing inks and varnishes photoinitiator. Examples of suitable photoinitiators are 1-hydroxycyclohexanone (Irgacure® 184 company Ciba Spezialita-tenchemie AG, Klybeckstrasse 141, P.O.Box CH-4002, Basel), 2-methyl-1-[4-(methylthiophenyl)-2-morpholinopropan]-1-on (Irgacure® 907 company Ciba), 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone (Irgacure® 2959 company Ciba), a-dimethoxy-a-phenylacetophenone (Irgacure® 651 company Ciba), 2-benzyl-2-dimethylamino-1-(4-morpholinomethyl)butane-1-on (Irgacure® 369 company Ciba), bis(2,4,6-trimethylbenzoyl)phenyl-phosphine oxide (Irgacure® 819 company Ciba), 2-hydroxy-2-methyl-L-phenyl-L-propanone (Darocur® 1173 company Ciba), isopropylthioxanthone (IT company Lambson), 2 chlorothioxanthone (MMS product firms Lamb-son), benzophenone, 2,4,6-trimethylbenzenesulfonamide (product SRW BASF), ethyl-2,4,6-trimethylbenzenesulfonyl (product TPO-L BASF) and methylbenzofuran (product MBF firm Lambson), and the above list is not limited to the designated representatives.

The number of added photoinitiator largely depends on its type, as well as from the print method.

The total number of photoinitiators in the range of from 1 to 20 wt. -%, preferably from 2 to 10 wt. -%, particularly preferably from 3 to 7% mass calculated on the total weight of the printing ink or printing varnish.

Additionally, you can also use the joint initiators such as amines (for example, product MDEA Basf Aktiengesell-all, Carl-Bosch-StraBe 38, 67056 Ludwigshafen) or modified amines acrylates (for example, Ebecryl P115, Ebecryl 7100 firm Surface Specialities UCB; Actilane 705, Actilane 715, Actilane 755 Akzo Nobel Resins bv., sales Department, Germany Industriestr. 8. 46446 Emerly; Laromer PO 94 F Laromer LR 8869 BASF; Craynor 503, Craynor 550 company Cray Valley; Photomer 4775F company Cognis), the number of which depending on the type and printing method is from 0.5 to 20% wt. in terms of the total weight of the printing ink or printing varnish.

As photoinitiator preferably using bis(2,4,6-trimethylbenzoyl)phenylphosphine (Irgacure® 819 company Ciba), 2-guide is hydroxy-2-methyl-1-phenyl-1-propanone (Darocur® 1173 company Ciba) and trimethylbenzenesulfonamide (product SRW BASF).

In addition, in the printing ink or printing varnish may be present thickener selected from the group waycause commonly used in printing inks and/or print varnishes thickeners. To fit the thickeners include, for example, pyrogenic silica, optionally treated metallicana layered silicates and derivatives of castor oil with a modified structure, as well as solutions of modified urea or amides paligid-roxicet with carboxyl groups, and the above list is not limited to the designated representatives. The amount of thickener (used thickeners) is usually in the range from 0 to 10 wt. -%, preferably from 0.5 to 5 wt. -%, first of all, 1.5 to 3 wt%. in terms of the total weight of printing ink, respectively, of the printing lacquer.

In the General case, the printing ink or printing varnish also contain the non and/or contributing to the bottling facility.

Antispyware can be selected from the group including, for example, modified acrylates, modified copolymers of acrylates and siliconsamurai connection, without limitation specified compounds. Suitable contributing to the filling means are, for example, modified polyacrylates and polysiloxanes.

Antispyware and str is obstrusive bottling funds depending on their type and method of printing in General used in amounts of from 0.1 to 2.5 wt%. in terms of the total weight of printing ink, respectively, of the printing lacquer.

In order to avoid migration of antispyware and contributing to the filling means and the resulting possibility of exfoliation of the molded products from the paint layer as compounds of this type are preferably used does not contain silicones products.

As the stabilizer is preferably used Genorad 16 firms Rahn, and Fluorstab UV2 company Kromachem (10, Park Industrial Centre, Tolpits Lane, Watford, Hertfordshire WD1 8SP, UK), without limitation specified connections.

Printing ink, respectively printed lacquer may contain one or more fillers. Fillers are used to reduce rates and optimization of fluid properties of printing inks and/or printing varnish.

The properties of the fillers are not particularly critical. The fillers can be selected from the group including commonly used in printing inks substances, such as white porcelain clay, barium sulfate (precipitated state planfix), calcium carbonate, zinc sulfide, silica, talc, aluminum silicate, aluminum hydroxide and/or silica gel, and possible fillers are not limited to the above. The amount of filler used in the range of from 0 to 50 wt. -%, preferably from 0 to 30 wt. -%, for example, 20% of the mass. in the recalculation of the total weight of the printing ink or printing varnish.

Under preferably contained in printing ink pigments imply any pigments. As pigments can be used, for example, titanium dioxide, zinc sulfide, carbon black pigment, asocially yellow, isoindoline yellow, dialled orange, chinagreen purple, diatopically red, copper phthalocyanine blue, copper phthalocyanine green, dioxazine purple or dilatometric with pigments not organicists above.

An indicative list of other pigments that can be used according to the invention, are listed in the International Handbook of color indicators (4th edition online, 2001, a joint publication of the society of professionals in the field of dyeing and colour design and the American Association of chemical technology and color science textiles).

According to the invention can also be used for effect" pigments, such as mica with metal oxide coated metal pigments, and others. The amount of the color pigment is usually from 1 to 50 wt. -%, preferably from 3 to 45 wt%. in terms of the weight of the printing ink and depends on the type of pigment required coverage and the selected printing method. The white pigment is usually used in an amount of from 20 to 50 wt. -%, preferably from 25 to 45% of the mass. Colored pigments such as p is avilo used in an amount of from 1 to 20 wt. -%, which depends on the type and hue of the color pigment, and from the print method.

Mica with metal oxide coated metal pigments generally used in amounts of from 1 to 20 wt. -%, which depends on the type and hue of the color pigment, and from the print method.

All pigments used must have extremely high thermal stability and should not destructivity, wagonette or change the color tone in the temperature conditions of the subsequent injection molding.

To improve properties in paint you can also add wax. Suitable waxes are commercially available products. Primarily suitable are the following commercially available wax below as examples (in brackets the supply source).

Polyethylene wax:

Ceraflour 990 and Ceraflour 991 (company Byk-Cera; Danzigweg 23; 7418 EN Deventer, the Netherlands), Printwax ME 0825 (firm Deurex Micro-Technologies GmbH; Dr. Bergius Strasse 18/20; 06729 Tragic, Germany).

Modified polyethylene wax:

Ceraflour 961 (company Byk-Cera; Danzigweg 23; 7418 EN Deventer, the Netherlands), Everglide UV 961 25% (firm Krahn-Chemie GmbH; Grimm 10; 20457 Hamburg, Germany).

Polyethylene wax, high density:

Ceraflour 950 (company Byk-Cera; Danzigweg 23; 7418 EN Deventer, the Netherlands).

Connection type polymer-silica gel:

Deuteron MM 659 (Deuteron GmbH; Ellern 2; 28832 Achim, Germany). Mikronizirovanny the polyolefin wax:

Micro Wax DM and Micro Wax HTDM (firm Finma-Chemie GmbH, The-odor-Heuss-Strasse 5; 61191 Rosbach, Germany.

Wax by Fischer-Tropsch:

Ceraflour 940 (company Byk-Cera; Danzigweg 23; 7418 EN Deventer, the Netherlands).

Micronized polytetrafluoroethylene wax:

Ceraflour 980 (company Byk-Cera; Danzigweg 23; 7418 EN Deventer, the Netherlands), Ultraglide UV 701 (firm Krahn-Chemie GmbH; Grimm 10; 20457 Hamburg, Germany), Shamrock ST-3 (firm Shamrock; Heesterveldweg 21; 3700 Tongeren, Belgium).

Micronized polytetrafluoroethylene/polyethylene wax:

Ceraflour 968 and Ceraflour 996 (company Byk-Cera; Danzigweg 23; 7418 EN Deventer, the Netherlands).

Amide wax:

Ceraflour 994 (company Byk-Cera; Danzigweg 23; 7418 EN Deventer, the Netherlands), Deurex MA 7020 (firm Deurex Micro-Technologies GmbH; Dr. Bergius Strasse 18/20; 06729 Tragic, Germany).

Carnauba wax:

Ceraflour 4RC 1165 (company Byk-Cera; Danzigweg 23; 7418 EN Deventer, the Netherlands), Everglide UV 636 25% (firm Krahn-Chemie GmbH; Grimm 10; 20457 Hamburg, Germany).

Mineral wax:

Deurex MM 8120 and Deurex MM 8200 (firm Deurex Micro-Technologies GmbH; Dr. Bergius Strasse 18/20; 06729 Tragic, Germany).

Micronized ester wax with UV reactive groups:

TP Ceridust 5091 (firm Clariant GmbH; Am Unisyspark 1; 65843 Sulzbach, Germany).

Paraffin wax:

Polyspers HP (company Eastman Chemical Deutschland GmbH; Charlottenstrasse 61; 5114 9 Cologne, Germany).

Polypropylene wax:

Crayvallack WN-1135 (firm Lubrizol Coating Additives GmbH; Max Planck Strasse 6; 27721 Ritterhude, Germany).

Micronized spray polyolefin wax:

Printwax MXF 9510 D and Printwax MX. 9815 D (firm Deurex Micro-Technologies GmbH; Dr. Bergius Strasse 18/20; 06729 Tragic, Germany).

The concentration of the wax is preferably from 0 to 10 wt. -%, more preferably from 0 to 3.0 wt. -%, particularly preferably from 0 to 2% of the mass. in terms of the mass of inks, respectively, of the printing lacquer.

To printing ink, respectively printing the lacquer before printing, you can add an adhesion promoter used in quantities of from 0.01 to 20 wt. -%, preferably from 1 to 10% of the mass. in terms of the weight of the paint or varnish. It is about the isocyanate adhesion promoters, for example, aliphatic polyisocyanates such as hexamethylenediisocyanate (HDI) or trimethylhexamethylene (TMHDI), cycloaliphatic the polyisocyanates, such as isophoronediisocyanate (IPDI), hydrogenated xylylenediisocyanate (HXDI) or diisocyanatohexane (HMDI), and aromatic polyisocyanates, such as tolylenediisocyanate (TDI), xylylenediisocyanate(h), tetramethyldisilazane (TMXDI) or diisocyanato-difenilmetana (MDI). The corresponding commercially available products are, for example, Desmodur E41 or Desmodur N 75 (Bayer). In addition, as adhesion promoters can be used polyimides, such as polyethylenimine or polycarb-diimide. Other suitable adhesion promoters are silane promoters, t is the cue as alkylsilane, vinylsilane, Methacrylonitrile, epoxysilane, aminosilane, carbamezepine, CHLOROSILANES or isocyanatobenzene, aminosilane, such as gamma aminopropyltriethoxysilane, gamma aminopropyltrimethoxysilane, N-beta-(aminoethyl)-gamma-amino-propyltrimethoxysilane, bis(gamma-triethoxysilylpropyl)amine, N-phenyl-gamma-aminopropyltrimethoxysilane or T-beta(aminoethyl)-gamma aminopropyltrimethoxysilane and isocyanatobenzene, such as gamma isocyanatopropyltrimethoxysilane.

To the preferred printing methods include screen printing, rotary screen printing, digital printing, flexografica printing, letterpress, offset printing and gravure printing. According to the invention is particularly preferably used a method of screen printing.

Thermoplastic polymers are particularly suitable for use as a substrate, on which is applied a layer of printing ink or printing varnish, and/or for subsequent fill proposed in the invention laminates are polycarbonates or copolycarbonates based diphenols, polyacrylates, spoliarium, polymethacrylates or copolymerisate, for example, preferably such as polymethylmethacrylate(emission spectra obtained for pure); polymers or copolymers of styrene, for example, preferably such as polystyrene (PS), copolymer of styrene with acrylic is nitrile (SAN) or ternary copolymer based on Acrylonitrile, butadiene and styrene (ABS);

thermoplastic polyurethanes; polyolefins, for example, preferably such as polypropylene, or polyolefin-based cycloolefins (e.g., Topas® company Hoechst); polymers obtained by polycondensation or copolycondensation terephthalic acid, for example, preferably such as polyethylene terephthalate (PET), spriterenderer (Soret)modified with glycol terephthalate (PETG), modified with glycol polycyclohexylenedimethylene (PSTG), modified with glycol solicitorgeneral modified with glycol polybutylene terephthalate(RHT) or modified with glycol copolymerisate (Sort); polymers obtained by polycondensation or copolycondensation naphthaleneboronic acid, for example, preferably such as polietilentereftalat (PEN); polymers obtained by polycondensation or copolycondensation at least one cycloalkylcarbonyl acid, for example, preferably such as politological-imetadataexchange acid (PCCD), polysulfones (PSU), as well as mixtures of the above polymers.

Preferred thermoplastic polymers are polycarbonates, copolycarbonates or a mixture containing at least one polycarbonate or copolycarbonate. Especially preferred is sustained fashion is a mixture, containing at least one polycarbonate or copolycarbonate and at least one polymer obtained by polycondensation or copolycondensation terephthalic acid, naphthaleneboronic acid or cycloalkylcarbonyl acid, preferably cyclohexanedicarboxylic acid. Even more preferred thermoplastic polymers are polycarbonates or copolycarbonates primarily products with srednevekovoi molecular mass Mwin the interval from 500 to 100,000, preferably from 10000 to 80000, particularly preferably from 15,000 to 40,000, or mixtures of these polycarbonates or copolycarbonates at least one polymer obtained by polycondensation or copolycondensation terephthalic acid, srednevekovaja molecular mass M which is in the range from 10,000 to 200,000, preferably from 26000 to 120,000.

To commonly used substrates at least one thermoplastic polymer, which method print put a layer of printing ink or printing varnish, include, in particular, polycarbonate, pre-treated complex polyester, a copolymer of Acrylonitrile, butadiene and styrene (ABS), polymethylmethacrylate (emission spectra obtained for pure), mixtures of polycarbonates with complex polyesters, and mixtures of polycarbonates with ABS copolymer, and the above list is not limited to what is shown in it representatives.

Suitable substrates can be, for example, a single-layer or multilayer. The multilayer substrate may consist of several polymer layers and/or one polymer layer and the coating of other materials. Suitable multilayer substrates are, for example, coextrudable films or laminates containing one or more of the above thermoplastic polymers, and is also provided with a coating film containing one or more of the above thermoplastic polymers.

Suitable film produces, for example, Bayer MaterialScience AG (Bayfol®, Makrolon®, Makrofol®, Bayblend®), as well as the Autotype company (Autoflex Hiform™, Autoflex Xtraform™). The substrate preferably using film of polycarbonate or mixtures of polycarbonates with complex polyesters.

Materials that can be used to implemented by the molding further fill put on a thermoplastic substrate layer of printing ink or printing varnish are, in particular, polyesters, polycarbonates, blends of polycarbonate, polystyrene, ABS copolymer, mixtures with ABS copolymer, polyamide, polyvinyl chloride (PVC), polymethylmethacrylate (emission spectra obtained for pure, as well as other polymeric materials. For the preferred materials for subsequent fill method of injection molding include polycarbonate and various mixtures with the polycarbonate.

Given the i.i.d. following examples serve for a more detailed explanation of the present invention and do not limit its scope.

Examples of carrying out the invention

Getting the polycarbonates according to the invention are suitable as binders

The polycarbonates of the formula (I-h) was prepared as follows.

Polycarbonate 1

In atmophere inert gas under stirring to prepare a solution KZT 205.7 g (0.90 mol) of bisphenol a (2,2-bis(4-hydroxyphenyl)propane), a 30.7 g (0.10 mol) of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 336,6 g (6 mol) of KOH and 2700 g of water. To the resulting solution was added a solution of 1.88 g of phenol in 2500 ml of methylene chloride. In a well-mixed total solution at pH 13 to 14 and a temperature of 21 to 25°C add 198 g (2 mol) of phosgene. Then add 1 ml of ethylpiperidine, and continue stirring for a further 45 minutes. Separate does not contain bisphenolate the aqueous phase, the organic phase after acidification with phosphoric acid is washed with water to neutral pH and freed from solvent. The relative viscosity of a solution of the polycarbonate is 1,255.

The glass transition temperature of the polymer, determined by the method of differential scanning calorimetry (DSC), is 157°C.

Polycarbonate 2

Similarly, the synthesis of polycarbonate 1 in polycarbonate turn the mixture 181,4 g (0,79 mol) of bisphenol a with of 63.7 g (0.21 mol) of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.

The relative viscosity of a solution of the obtained polycarbonate which leaves 1,263.

A certain method of DSC, the glass transition temperature of the polymer is 167°C.

Polycarbonate 3

Similarly, to obtain a polycarbonate 1 in polycarbonate turn mixture of 149.0 g (of 0.65 mol) of bisphenol a and 107,9 g (0.35 mol) of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.

The relative viscosity of a solution of the obtained polycarbonate is 1,263.

A certain method of DSC, the glass transition temperature of the polymer is 183°C.

Polycarbonate 4

Similarly, to obtain a polycarbonate 1 in polycarbonate turn mixture of 91.6 g (0.40 mol) of bisphenol a and 185,9 g (of 0.60 mol) of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.

The relative viscosity of a solution of the obtained polycarbonate 1.251.

A certain method of DSC, the glass transition temperature of the polymer is 204°C.

Polycarbonate 5

Similarly, to obtain a polycarbonate 1 in polycarbonate make a mixture of 44.2 g (to 0.19 mol) of bisphenol a and 250,4 g (0.81 mol) of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.

The relative viscosity of a solution of the obtained polycarbonate is 1,248.

A certain method of DSC, the glass transition temperature of the polymer is 216°C.

The glass transition temperature of the samples polycarbonate is determined by means of DSC in accordance with ISO 11357. Prior to determination of glass transition temperature of the samples within 24 hours, dried in a vacuum Cabinet.

P is the production used according to the invention stencil paints

Manufacturer of stencil paints is as follows.

First 20% massuanganhe Bayer Material Science polycarbonate 4, see above) is dissolved in 80% of the mass. 4-(1-oxo-2-propenyl)the research used as a UV-curable monomer. To a solution of the binder 4-(1-oxo-2-propenyl)morpholine add other monofunctional acrylates, diacrylate, photoinitiator, means to improve the filling, thickening agent and pigment, these components are pre-dispersed in dissolvere and processed using a three-roll or bead mill, receiving ink, the dispersion which is less than 10 microns.

Recipe of the respective stencil paints are shown in tables 1 and 2 and not ohranychytsya these examples.

Example 1 (according to the invention) Blue ink for screen printing

Table 1
Raw materialswt. -%
Polycarbonate 4 (20% wt.) 4-(1-oxo-2-propenyl)morpholine (80 wt. -%)72,00
1-Adenylation-2-heof 4.66
2-Phenoxyethylacrylate (Sartomer SR339EU)6,44
Critic decenteralized (Sartomer SR833S) 5,00
Polysiloxan (means to improve the filling)1,00
Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (photoinitiator)0,90
2-Hydroxy-2-methyl-1-phenyl-1-propane (photoinitiator)5,00
The solution of a modified urea (thickener)1,00
Persistent blue 15:3 249-1532 (pigment)4,00

Example 2 (according to the invention) White ink for screen printing

Table 2
Raw materialswt. -%
Polycarbonate 4 (20% wt.) 4-(1-oxo-2-propenyl)morpholine (80 wt. -%)27,90
1-Adenylation-2-he7,60
2-Phenoxyethylacrylate (Sartomer SR339EU)10,50
4-(1-Oxo-2-propenyl)morpholine1,10
Tricyclopentadiene (Sartomer SR833S)5,0
Polysiloxan (means to improve the filling)1,00
Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (photoinitiator)0,90
2-Hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator)5,00
The solution of a modified urea (thickener)1,00
Thione 595 (pigment)40,00

With the aim of producing proposed in the invention of layered materials on the polycarbonate film Makrofol® DE-4 thickness of 375 μm (Bayer MaterialScience AG) with the help of stencil tissue 150-31 perform the printing inks of examples 1 and 2 with a viscosity of about 4000 MPa·s (system of a cone-plate shear rate of 100/s) and at a speed of 15 m/min carry out the subsequent curing using two mercury lamps at 120 watts/see

Example 3 (according to the invention) Blue ink for screen printing

For the manufacture of other stencil paint 30% of the mass. spanning from Bayer MaterialScience AG (polycarbonate 5, see above) are dissolved in 70% of the mass. 4-(1-oxo-2-propenyl)of the research as a UV-curable monomer.

To a solution of the binder 4-(1-oxo-2-propenyl)morpholine add di is kilat, photoinitiator, means to improve the filling, thickening agent and pigment, these components are pre-dispersed in dissolvere and processed using a three-roll or bead mill, getting the paint with a particle size less than 10 microns.

The composition of the corresponding stencil paints are shown in table 3 and not ogranichetsya this example.

Table 3
Raw materialswt. -%
Polycarbonate 5 (30% wt.) 4-(1-oxo-2-propenyl)of the research (70% wt.)52,50
4-(1-Oxo-2-propenyl)morpholine25,60
Tricyclopentadiene (Sartomer SR833S)10,00
Polysiloxan (means to improve the filling)1,00
Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (photoinitiator)0,90
2-Hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator)5,00
The solution of a modified urea (thickener)1,00
Persistent blue 15:3 249-1532 (pigment)4,00

On the polycarbonate film Makrofol® DE-4 thickness of 375 μm (Bayer MaterialScience AG) with the help of stencil tissue 150-31 perform the printing ink of example 3 viscosity of about 4000 MPa·s (system of a cone-plate shear rate of 100/s) and at a speed of 15 m/min carry out the subsequent curing using two mercury lamps at 120 watts/see

For comparison with the prior art violet following comparative examples 4-7.

Comparative example 4 UV paint for graphic screen printing

Printing and curing is carried out analogously to examples 1 and 2, using as a substrate of polycarbonate film Makrofol® DE-4 thickness of 375 μm (firm Voeg MaterialScience AG) and commercially available stencil paint specified in table 4 composition containing as a binder polyacrylate.

Isobutylacetate
Table 4
UV ink for textile printing
Raw materialswt. -%
Copolymer of methyl methacrylate17,50
1-Adenylation-2-he9,00
35,00
2-Phenoxyethylacrylate (Sartomer SR339EU)6,00
Polysiloxan (means to improve the filling)1,00
2-Hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator)3,50
2-Benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)-1-butanone (photoinitiator)2,00
Isopropylthioxanthone (photoinitiator)0,70
Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (photoinitiator)1,30
Persistent blue 15:3 249-1532 (pigment)4,00
Barium sulfate (Sachtleben blanchis, micro)20,00

Comparative example 5 UV paint for graphic screen printing

Printing and curing is carried out analogously to examples 1 and 2, using as a substrate of polycarbonate film Makrofol® DE-4 thickness of 375 μm (Bayer MaterialScience AG) and commercially available stencil paint specified in table 5, which similarly to comparative example 4 contains as a binder polyacrylate./p>

Table 5
UV ink for textile printing
Raw materialswt. -%
Copolymer of methyl methacrylate24,00
1,6-Hexanediamine (Sartomer SR238)23,00
Isobutylacetate12,00
2-Phenoxyethylacrylate (Sartomer SR339EU)15,00
Polysiloxan (means to improve the filling)1,00
Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (photoinitiator)0,90
1-Hydroxycyclohexane (photoinitiator)7,00
Persistent blue 15:3 249-1532 (pigment)4,00
Barium sulfate (planfix, micro)13,10

Comparative example 6 UV paint for graphic screen printing

Printing and curing is carried out analogously to examples 1 and 2, using as for the spoons polycarbonate film Makrofol® DE-4 thickness of 375 μm (Bayer MaterialScience AG) and commercially available stencil paint specified in table 6 composition, containing as a binder polyurethanebased.

Table 6
UV ink for screen printing
Raw materialswt. -%
Polyurethanebased46,00
1-Adenylation-2-he9,00
Isobutylacetate22,00
Polysiloxan (means to improve the filling)1,00
Isopropylthioxanthone (photoinitiator)1,00
2-Methyl-1-[4-(methylthio)phenyl]-2-(morpholinyl)-1-propanone (photoinitiator)2,00
Persistent blue 15:3 249-15324,00
Barium sulfate (planfix, micro)15,00

Comparative example 7 UV paint for casting in mold

Printing and curing is carried out analogously to examples 1 and 2, using as a substrate of polycarbonate film Makrofol® DE-4 thickness of 375 μm Bayer MaterialScience AG and commercially available t aparatow paint Decomold™ firm Coates, which the binder contains a copolymer with the main chain of Alif-political and oligomeric polycarbonate urethaneacrylate side chains.

Example 8 the Results of tests of suitability for molding

Assessment of the suitability manufactured in examples 1-7 films coated (laminated material) for forming is as follows.

Formability explore by car SAMK 360 firms Niebling for molding under high pressure (year 2000). Experiments to assess the suitability of the material for molding is carried out, using a mold with Windows for heating/ventilation. Molded item with dimensions 190×120 mm equipped with various slots designed to evaluate the strain.

The mold temperature is 100°C. the Film before forming is subjected to heating in the preheating zone. The duration of heating for all experiments is 16 seconds, thus raising the temperature of the film to about 150-160°C. Evaluation of the suitability of films for molding is carried out on the basis of the results of testing five samples for each example.

The results of the visual assessment of the suitability of films for molding are shown in table 7.

Molding at high pressure
Table 7
ExampleStretchingAssessment (formation/extension)
1SatisfactorySatisfactory+/+
2SatisfactorySatisfactory+/-
3SatisfactorySatisfactory+/+
4SatisfactorySatisfactory+/+
5SatisfactoryCracks+/-
6SatisfactoryStrong tremino-education+/-
7The viscosity at 80°CSatisfactory-/+

In table 7 the data show that in addition to the proposed invention is laistigh materials forming and stretching without damage to the laminate as a whole or only the ink film to be only a material of comparative example 4.

Example 9 Study further casting molding

Made in accordance with examples 1-7, provided with a coating and subjected to a molding according to example 8 films (laminates) have, as described below, for suitability to the application of a polymeric coating method subsequent injection molding. To perform sootvetstvujushij experiments it is possible to use a film similar to that used to assess the suitability for processing.

Experiments carried out on the injection molding machine company Arburg. Maximum closing force on the injection molding machine Arburg Allrounder 570 (year 2003) is 200 tons. For subsequent application to a variety of films, carried out by the method of injection molding at 260°C, a mixture of polycarbonate with ABS. The filling of the mold is 2 seconds, the unit pressure of 1000 bar. The mold temperature in all experiments is set at 60°C. the Mold is equipped with a hot channel through which the polymer through the cold dispenser through the subsidiary Zapf enters the socket of the mold. This raises the high temperature and shear loads, an excessive amount of which can result in partial leaching of the paint layer.

Adhesion applied by subsequent injection molding of the polymer to a paint layer OC is Nivat by manual exfoliation.

The results of the experiments with the subsequent molding (visual assessment) are given in table 8.

Table 8
ExampleLeachingAdhesionAssessment (leaching/adhesion)
1NoHigh+/+
2NoHigh+/+
3NoHigh+/+
4Strong washoutNo-/-
5NoLow+/-
6NoNo+/-
7NoNo +/-

In table 8 the data show that the subsequent injection molding without washing out the paint layer with high adhesion molding polymer sealed to thermoplastic polymer can be performed only for the proposed in the invention of layered materials.

Example 10 the Results of environmental testing

Molded parts from example 9 with the purpose of further evaluating the adhesion between the sealed film (layered material) and material damage by subsequent injection molding, is exposed to the climate challenge. Climatic tests carried out in a climatic Cabinet company Weiss (year vypuska) under the following conditions: temperature 80°C, humidity 85%, storage duration 100 hours.

Then carry out a visual assessment of the films, as well as manual exfoliation caused by the injection molding of the polymer. The results of the respective tests are shown in table 9.

Table 9
ExampleThe condition of the materialAdhesionEvaluation (state /adhesion)
1SatisfactoryH is Kaya +/+
2SatisfactoryHigh+/+
3SatisfactoryHigh+/+
4*Not testedNot testedThe lack of evaluation
5Many shellsNo-/-
6Many shellsNo-/-
7ShellNo-/-

In accordance with those reported in table 9 the data in a satisfactory condition and high adhesion after storage in a climate Cabinet are characterized by only offered in the invention of layered materials. In comparative examples found pitting and lack of adhesion.

A) note: laminates of comparative example 4 were subjected to climatic tested the tion, because of unsatisfactory results for the corresponding sample were obtained already when tested in accordance with example 9.

The overall score

Joint consideration of the results of examples 8-10, i.e. the total production chain, including the formation and deposition of polymer on sealed film (laminates) by subsequent injection molding, results shown in table 10 overall picture for the samples of examples 1-7.

Table 10
ExampleMoldingThe final injection moldingClimatic testScore
1SatisfactorySatisfactorySatisfactory+
2Minor crackingSatisfactorySatisfactory+
3SatisfactorySatisfy the recreational Satisfactory+
4SatisfactoryLeachingNot tested-
5CracksLow adhesionShell-
6CracksThe lack of adhesionShell-
7StickinessThe lack of adhesionShell-

Proposed in the invention of layered materials of examples 1-3 is observed optimal formability, the ability to stretch in forming and suitability for subsequent filling by injection molding. These materials are characterized by high adhesion caused the subsequent molding material sealed to the film (proposed in the invention, the layered material) directly after performing the subsequent injection molding, and after storage de-molded the Aley in a climatic chamber, and no leaching of the dye from the ink layer. In accordance with the comparative examples 4-7 already in forming detect relatively high cracking in the ink film or the adhesion of the aggregate of the layered material to a tool for molding. In all comparative examples, when the subsequent filling by injection molding and stored in a climatic chamber found strong leaching of the dye from the ink layer or the lack of sufficient adhesion between accompanied with colorful coating film and coated molding material.

Example 11

Table 11 provides additional examples of the cyan ink colors applied other methods of printing, and the options of colors are not limited to, are listed in table 11 examples.

Table 11
Examples of blue dyes for printing different methods
Raw materialsStencil
Naya print
Rotary screen printingFlexografica printDigital printing
Polycarbonate 4 (30%) 4-(1-oxo-2-propenyl)morpholine (70%) 31,0015,405,00
Polycarbonate 5 (35%) of 4-(1-oxo-2-propenyl)morpholine (65%)41,00
Aliphatic diacrylate (80%) in DIPROPYLENE-cardiacrelated(20%)5,00
4-(1-Oxo-2-propenyl)morpholine4,008,6023,00
1-Adenylation-2-he18,0016,0015,5019,00
2-Phenoxyethylacrylate (SR339EU)24,1022,0021,0026,00
1,6-Hexanediamine5,005,005,005,00
Polysiloxan1,00 0,10
Atilirovanie the non (no silicones)2,502,50
Solsperse 50000,100,400,05
Solsperse 390000,401,600,20
The solution of a modified urea1,00
2-Hydroxy-2-methyl-1-phenyl-1-propanone5,007,507,50
1-hydroxycyclohexyl-niketan7,50
Diphenyl(2,4,6-trimethyl-benzoyl)phosphine oxide7,507,507,50
Phenylbis(2,4,6-trimethyl-benzoyl)phosphine oxide0,90
Persistent blue 15:3 249-15324,004,00
Hostaperm blue B2G15,001,65

1. Layered material, including:
a) a substrate of at least one thermoplastic polymer, preferably a film of at least one thermoplastic polymer,
b) single-layer or multilayer colorful and/or lacquer film of at least one of printing ink or a printed varnish containing:
as a binder at least one non-radiative curing aromatic polycarbonate based on gemenele disubstituted dihydroxydiphenylsulfone and
as solvent at least one radiation curable monomer selected from the group comprising acrylates, methacrylates, simple vinyl esters and nitrogen-containing compounds with ethylene double bond,
characterized in that the binder dissolved in the melt is e, after curing remains in the printing ink or printing varnish in chemically cross-linked state.

2. The layered material according to claim 1, characterized in that the glass transition temperature of polycarbonate is used as a binder in a colorful, respectively lacquer film above the glass transition temperature of the substrate, the first thermoplastic polymer film.

3. The layered material according to claim 1, characterized in that under thermoplastic polymer substrate involve one or more polycarbonates or copolycarbonates based diphenols, polyacrylate(s), spoliarium(s), polymethacrylate(s), copolymerisate(s), polymer(s) or copolymer(s) of styrene, the polymer(s)obtained(e) condensation or copolycondensation terephthalic acid, naphthaleneboronic acid or cycloalkylcarbonyl acid, polyurethane(s), the polyolefin(s), or mixtures of these polymers.

4. The layered material according to claim 1, characterized in that the total thickness of the substrate and colorful, respectively varnish film is from 0.05 to 4 mm, preferably from 0.1 to 2 mm, particularly preferably from 0.2 to 2 mm.

5. The layered material according to claim 1, characterized in that the substrate consists of one or more polymer layers and/or colorful film consists of one or several layers.

6. The layered material according to claim 1, characterized in that the polycarbonate binder in a printing ink or printing varnish has srednevekovoi molecular weight Mw of at least 10,000 and/or contain bifunctional carbonate structure

in which
R1and R2mean hydrogen, halogen, alkyl with 1-8 carbon atoms, cycloalkyl with 5-6 carbon atoms or aralkyl with 6-10 carbon atoms,
m means an integer from 4 to 7,
R3and R4independently of one another denote hydrogen or alkyl with 1-6 carbon atoms, chosen individually for each X, and
X mean carbon
provided that the residues R3and R4attached to at least one atom X, simultaneously denote alkyl.

7. The layered material according to claim 6, characterized in that the polycarbonate contains at least 30 mol.% bifunctional carbonate structural units of the formula (I) in terms of quantity all containing bifunctional carbonate structural units.

8. The layered material according to claim 1, characterized in that the softening temperature of the radiation utverzhdenii printing ink or printing varnish is less than 144°C, preferably less than 120°C, more preferably less than 100°C.

9. Laminate according to one of claims 1 to 8, characterized in that it is molded material.

10. A method of manufacturing laminated material according to one of claims 1 to 9, characterized in that on a substrate, the first film of thermoplastic polymer, method of printing, especially screen printing, are colorful and/or varnish the layer, which is then subjected to radiation curing.

11. The method according to claim 10, characterized in that the substrate before application of a colorful and/or a lacquer layer or a laminated material after application to the substrate colorful and/or a lacquer layer is subjected to molding.

12. Moulded, followed by pouring, characterized in that the sealed printing ink or printing varnish side of the layered material according to one of claims 1 to 9 subjected to single or multiple subsequent filling of at least one thermoplastic polymer with a temperature of 200°C or higher.

13. Moulded, followed by pouring in item 12, characterized in that the layered material according to one of claims 1 to 9 subjected to the subsequent fill one or more layers of at least one thermoplastic polymer.

14. A method of manufacturing molded parts, followed by pouring in item 12 or 13, characterized in that the sealed printing ink or printing varnish side of the laminate produced by the method according to claim 10 or 11, is subjected to a single or multiple subsequent filling of at least one thermoplastic polymer at a temperature of 200°C or higher.

15. The method according to 14, wherein the next fill is carried out by injection molding, molding or foaming, predpochtitel is but by injection molding.

16. The method according to 14 or 15, characterized in that the sealed printing ink or printing varnish side of the laminate produced by the method according to claim 10 or 11, a method of printing, especially screen printing, applied polyurethane coating, and then perform subsequent fill at least one thermoplastic polymer.



 

Same patents:

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: curable polymer composition contains a linker which contains at least one organic polymer with silane groups, having molecular weight higher than 1000, and selected from a group of polymers consisting of aromatic or aliphatic polyurethanes which are partially or completely fixed with silane, polyethers and polyesters, polycarbonates, polyacrylate, polybutadiene, polyether with hydrolysable silane groups and mixtures thereof, at least one reactive polyorganosiloxane polymer having molecular weight from about 1000 to about 200000 and, optionally, an organic polymer without functional silane groups.

EFFECT: improved weather resistance.

15 cl, 4 ex

FIELD: polymers, paint and varnish materials.

SUBSTANCE: invention relates to polycarbonate-base compositions used for applying covers. Polymeric paint and varnish composition comprises the following components, mas. p. p.: polycarbonate based on bisphenol A with molecular mass 26000-36000 Da, 12.0-14.0; polymeric adhesive as a plasticizer, 1.5-4.2; copolymer acrylonitrile-butadiene-styrene, 0.12-1.4; mineral filling agent chosen from the group of mineral small-dispersed materials: aluminum powder, titanium dioxide, alkali-earth metal salts, talc, microwollastonite, 0.6-26.0; dye chosen from the order of phthalocyanine dyes or color mineral pigments, 0.1-1.4; polyoxyethylene sorbitan monooleate (Tween-80) as a surfactant, 0.001-0.01, and chlorinated aliphatic solvent, the balance. Invention provides the development of polymeric paint and varnish composition rapidly drying in natural conditions that allows preparing arbitrarily colored covers on different building materials being without deterioration of adhesion.

EFFECT: improved and valuable properties of composition.

3 cl, 1 tbl, 9 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention proposes a method for preparing vinylene carbonate mixture. Method involves interaction of monohaloethylene carbonate of the formula (II): wherein X means halogen atom with a dehydrohalogenating agent at temperature in the range 40-80°C but preferably at 60°C in organic solvent medium wherein ethylene carbonate is used as an organic solvent. As a dehydrohalogenating agent method involves using amine, in particular, trialkylamine but preferably triethylamine, and monochloroethylene carbonate is used as monohaloethylene carbonate preferably. Interaction is carried out in inert gas atmosphere preferably. Invention provides preparing vinylene carbonate mixture by a simple and economy method with the high content of vinylene carbonate in the end product. Method provides easily isolation of vinylene carbonate from the prepared mixture by distillation off, for example, under vacuum in the film evaporator. Also, invention relates to a crude vinylene carbonate mixture prepared by above described method that is designated as an additive for lithium-ionic batteries as a component of surface coating material as a monomer for preparing polyvinylene carbonate.

EFFECT: improved preparing method.

7 cl, 3 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: dyes.

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

EFFECT: improved properties of dye, improved preparing method.

14 cl, 6 ex

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: invention relates to magnetic compositions used as ink or toner for producing pigmented magnetic materials. The magnetic composition contains particles having a core made of magnetic material and a coating surrounding the core. The pigmented magnetic layer on the substrate has a Hunter Lab colour scale L-value of at least 50. The coating of each particle is sufficiently opaque so as to completely conceal the colour of said core or an additional coating under said coating. Described also is a method of forming a pigmented magnetic layer, the obtained articles, e.g. banknotes, the protective property of the magnetic layer for the banknote.

EFFECT: disclosed magnetic compositions contain particles which are coated such that they look white, substantially white or coloured, while providing the desired magnetic properties and opening up new possibilities of producing corresponding magnetic layers on substrates.

24 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: polymer composition contains a first basic polymer (A) containing at least a thermoplastic polymer; a second basic polymer (B) containing at least a thermoplastic polymer and which is incompatible with the first basic polymer (A); and an additive (C) containing at least a substance which is incompatible with any of the first basic polymer (A) and the second basic polymer (B). The additive (C) is a liquid or suspension at temperature lower than the pyrolysis temperature of the first basic polymer (A) and the pyrolysis temperature of the second basic polymer (B). Components (A), (B) and (C) are separated from each other by a phase, and boundary surfaces, each lying between two phases (A), (B) and (C), are in contact with each other, forming spatially continuous parallel boundary surfaces. A moulded product, for example, is a filter or a spacer for refrigerators or capacitors. The polymer composition is used to produce an adhesive, ink, paint, films and fibre for a powdered catalyst.

EFFECT: polymer composition and products therefrom quasi-stably contain a large amount of substance which is incompatible with a polymer matrix, therefore suitable for obtaining moulded articles and other products having various properties.

25 cl, 10 ex

Liquid hardening // 2447114

FIELD: chemistry.

SUBSTANCE: invention relates to curing agents for air-drying alkyd-based resins, coating compositions, such as paint, varnish, wood stain, inks and linoleum floor coverings. Described is a curable liquid medium containing a) from 1 to 90 wt % of an alkyd-based resin and b) from 0.0001 to 0.1 wt % of a siccative in form of an iron or manganese complex with a tetradentate, pentadentate or hexadentate nitrogen donor ligand.

EFFECT: said siccative has high activity and enables hardening of compositions at relatively low concentration in a curable liquid medium.

19 cl, 8 tbl, 5 ex

FIELD: printing industry.

SUBSTANCE: proposed ink composition for inkjet printing includes a polyurethane material having an average molecular weight of from about 50000 to about 500000, in an effective amount of from about 0.2 wt % to about 5 wt %. The composition also includes a solvent in an effective amount of from about 5 wt % to about 20 wt %, and an anionic surfactant in an effective amount of from about 0.01 wt % to about 3 wt %. Also a method of creation of this ink composition and an ink jet printing system, comprising a substrate and the indicated ink composition is provided.

EFFECT: proposed ink composition for ink jet printing provides improved readiness for publication in an open state.

6 cl, 3 tbl, 13 ex

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

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

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