Method of producing polycarbonate multilayer composite

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

 

The invention relates to a method of manufacturing a composition containing:

a) from 0.1 to 20% by weight of the organic polymer, b) from 30 to 99.9% by weight of the solvent, C) from 0 to 10% by weight, relative to the dry weight, of the dye or mixture of dyes, d) from 0 to 10% by weight of the functional material or a mixture of functional materials, e) from 0 to 30% by weight of additives and/or auxiliary substances, or mixtures of such substances, the sum of components a) to d) is always 100% by weight, as inks for inkjet printing.

In addition, the invention relates to a method of manufacturing a composite material with interposed between two polycarbonate layers layer for inkjet printing, obtained by this way, the composite, the use of such a method for manufacturing a valuable document and/or protected against forgery of the document, as well as manufactured thus protected from a fake document and/or valuable document.

Background of invention and prior art

Composition for use as an ink for inkjet printing are known, for example, from a literary source EP 1690903 A. When it comes to ink water-based for use on absorbent substrate, such as, for example, postal envelopes. If provided an organic polymer, it is not as with sousage, and as additives for installation viscosity. Such ink is unsuitable for printing on polycarbonate film for the reasons explained below in relation to protected against forgery and/or valuable documents on a paper basis.

Personalization is protected against forgery and/or valuable documents on the polycarbonate-based takes place through the so-called method of laser engraving, in which due to optical/thermal interactions of the material is protected from a fake document and/or valuable document with laser radiation locally occur pyrolysis processes high resolution, and thus due to the formation of carbon appear local darkening. The disadvantage of this method is the limitation of the black-and-white images or, in the best case, the grayscale images.

Became well-known color personalization method of inkjet printing for documents on a paper basis is still not able to gain a foothold to secure documents from counterfeiting elements and/or valuable documents on the polycarbonate base. This is based, firstly, on the lack of compatibility of the used polymers/binders (in conjunction with the other ink components, such as colorants, additives, solvents) from the floor of the carbonate. This applies, for example, binders, known from literary sources "encyclopedia of industrial chemistry Ullman" (Ullmann''s Encyclopedia of Industrial Chemistry), electronic publication 2007, publisher Willey, head of the "Technology of imaging, printing ink for inkjet printer", and "encyclopedia of industrial chemistry Ullman", electronic publication 2007, publisher Willey, head of the "Paints and coatings", such as nitrocellulose, esters cellulose acetate-butyrate cellulose, CAB), polyacrylates, polyesters, epoxides, and much more. Secondly, a polycarbonate film with printing such inks are difficult to lamination. A polycarbonate film coated on the entire surface of the printing is practically not suitable for lamination, because the paint layer is a separating layer. When only a partial print there is a risk of the local delaminated. Thirdly, the polycarbonate has no absorptive ground surface. Ordinary ink for inkjet printers designed for a good time absorbed in the paper when printing on non-absorbent polycarbonate film they remain on the surface and after drying can sometimes completely socalists without a trace, as the paint is not absorbed into the material. Fourth, the layers of inkjet printing show among izvestnyh in this respect ink insufficient temperature stability. Because the region is protected against forgery and/or valuable documents polycarbonate film with printed, as a rule, are glued to each other under pressure (>2 bar) and temperature (>160° C), there is a risk of discoloration layer inkjet printing.

From a literary source EP 0688839 B1 famous ink for screen printing on the basis of disubstituted dihydroxydiphenyl-cycloalkanes. This literary source can also get a method of manufacturing such polycarbonates. Thus, this source of literature fully included in the scope of the disclosure of this application. However, ink for stencil printing according to all the rules cannot unconditionally be used in inkjet printers because inkjet printing has special requirements to be applied to the ink in communication with the spray technology printheads.

The technical problem of the invention

Thus, the basis of the invention lies in the technical problem of developing tools that will allow the use of inkjet printing in the framework of the manufacture of counterfeit documents and/or valuable documents on the basis of the polycarbonate polymer layers and apply layers of inkjet printing on such layers that satisfy all optical requirements, first of all can be colored, p. and this lamination their optical properties are not deteriorated, and which do not act as a separating layer in the lamination, and perhaps even contribute to the formation of monolithic composite of the polymer layers.

The main characteristics of the invention and the preferred forms of implementation

To solve this technical problem the invention proposes the use of a composition containing: a) from 0.1 to 20% by weight of a binder with a polycarbonate derivative based on gemenele disubstituted dihydroxydiphenyl-cycloalkane, b) from 30 to 99.9% by weight of the solvent or mixture of solvents) from 0 to 10% by weight, referred to the dry weight, of the dye or mixture of dyes, d) from 0 to 10% by weight of the functional material or a mixture of functional materials, e) from 0 to 30% by weight of additives and/or auxiliary substances, or mixtures of such substances, the sum of components a) to d) is always 100% by weight, as an ink for inkjet printing.

The invention is primarily based on the established fact that applied in accordance with the invention, the polycarbonate derivatives have high compatibility with polycarbonate substances for films, especially with polycarbonates based on Bisphenol a, such as, for example, film Makrofol©. High compatibility manifests itself in the fact that applied in accordance with the invention, the layer for inkjet printing with polycarb innymi derivatives connected with polycarbonate substances films in monolithic connection. The boundary layer between the materials after laminating optically no longer apparent. In addition, the polycarbonate derivative is resistant to high temperatures and does not show discoloration under typical lamination temperatures up to 200°C and more. In addition, it has been unexpectedly discovered that known for screen printing the composition of the paint (when adaptation viscosity) in respect of used binders is also suitable for inkjet printing. Finally, as a positive properties, it was found that painting means of the composite absorbed in the polymer layer with printed so deposited on the surface of the polymer layer is a printed layer cannot be removed without damage. Thus, applied in accordance with the invention compounds are suitable, for example, including, for personalization surface is protected against forgery and/or valuable documents, since the print on the polymeric layer is formed of an integrated composite.

As a result, by means of the invention that is protected from a fake document and/or valuable document based on the polycarbonate film can be provided with color printing, for example during personalization, such as the picture in the passport, with a layer for inkjet printing and acts not only as a separating layer, but apart from this even contributes to the formation of monolithic connection during lamination.

First of all, the polycarbonate derivative may contain functional structural units of carbonates according to the formula (I),

where R1and R2independently of one another represent hydrogen, halogen, preferably chlorine or bromine, With1-C8-alkyl, C5-C6-cycloalkyl,6-C10-aryl, preferably phenyl, and C7-C12-aralkyl, preferably, phenyl-C1-C4-alkyl, especially benzyl, m is an integer from 4 to 7, preferably 4 or 5, R3and R4individually selectable for each X, independently from each other hydrogen or C1-C6-alkyl, X is carbon, and n denotes an integer greater than 20, with the proviso that at least one atom X, R3and R4simultaneously denote al Kil.

Preferably, if from 1 to 2 atoms X, first of all, only one atom X, R3and R4at the same time are alkilani. First of all, R3and R4can be metelli. Atoms X in alpha - position to the diphenyl-substituted atom With (C1) cannot be disonesty alkilani Atoms X in the beta position relative To can be disonesty alkilani. Preferably, if m=4 or 5. Polycarbonate derivatives which may be formed, for example, based on monomers such as 4,4'-(3,3,5-trimethylcyclohexane-1,1-diol)-diphenol, 4,4'-(3,3-dimethylcyclohexane-1,1-diol)-diphenol or 4,4'-(2,4,4-trimethylcyclopentanone-1,1-diol)-diphenol.

Used according to the invention the polycarbonate derivative may, for example, be made according to the literary source DE 38 32 396.6 from diphenols by the formula (Ia), the disclosure of which is therefore fully included in the scope of the disclosure of this specification.

Can be used as diphenol by the formula (Ia) with formation of homopolymerization, as well as several diphenols by the formula (Ia) with formation of copolycarbonates (value residues, groups and parameters as in the formula (I).

In addition, divinely by the formula (Ia) can also be used in conjunction with other diphenolate, for example by the formula (Ib)

for manufacturing homomolecular, aromatic derivatives of polycarbonates.

Other suitable divinely by the formula (Ib) are those in which Z is an aromatic residue with 6 to 30 C atoms, which may contain one or more aromatic nuclei, may be substituted and may contain aliphatic residues or other than in the formula (Ia), cycloaliphatic residues or heteroatoms as connecting elements.

An example is mi diphenols by the formula (Ib) are: hydroquinone, resorcinol, dihydroxydiphenyl, bi-(hydroxyphenyl)-cycloalkanes, bis-(hydroxyphenyl)-cycloalkanes, bis-(hydroxyphenyl)-sulfides, bis-(hydroxyphenyl)-ethers, bis-(hydroxyphenyl)-ketones, bis-(hydroxyphenyl)-sulfones, bis-(hydroxyphenyl)-sulfoxidov, alpha, alpha'-bis-(hydroxyphenyl)-diisopropylbenzene, as well as their alkylated and halogenated in the nucleus of the connection.

These and other suitable divinely described, for example, in the literary sources US-A 3028365, 2999835, 3148172, 3275601, 2991273, 3271367, 3062781, 2970131 and 2999846, in the literature DE-1570703, 2063050, 2063052, 2211956, Fr-A 1561518 and in the monograph "X. Schnell, Chemistry and physics of polycarbonates" / N. Schnell, Chemisty and Physics of Polycarbonates, Interscience Publishers, new York 1964", which therefore fully included in the scope of the disclosure of this application.

Other preferred diphenols include, for example: 4,4'-dihydroxydiphenyl, 2,2-bis-(4-hydroxyphenyl)-propane, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4-hydroxyphenyl)-cyclohexane, alpha, alpha-bis-(4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis-(3-methyl-4-hydroxyphenyl)-propane, 2,2-bis-(3-chloro-4-hydroxyphenyl)-propane, bis-(3,5-dimethyl-4-hydroxyphenyl)-methane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-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, alpha, alpha-bis-(3,5-dimethyl-4-hydroxyphenyl)-R-is isopropylbenzo, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane and 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane.

Particularly preferred diphenolate by the formula (Ib) 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. Above all, preferred is 2,2-bis-(4-hydroxyphenyl)-propane. Other divinely can be used both separately and in compounds.

The molar ratio of diphenols by the formula (Ia) to be used when necessary to other diphenols by the formula (Ib) should be between 100 mass% (Ia) to 0% by weight (Ib) and 2% by weight of (Ia) to 98% by weight (Ib), preferably, between 100 mass% (Ia) to 0% by weight (Ib) and 10% by weight of (Ia) to 90% by weight (Ib) and, above all, between 100 mass% (Ia to 0% by weight (Ib) and 30 mass% (Ia) to 70% by weight (Ib).

High molecular weight polycarbonate derivatives of diphenols by the formula (Ia), optionally in combination with other diphenolate, can be produced by a known method of manufacture of polycarbonates. Thus, various divinely can be connected to each other as statistically and chunked.

Used in accordance with the invention, the polycarbonate derivatives can be branched known in itself. When branching the two is to be desired, it is possible in a known manner by the condensation of small amounts, preferably amounts between 0.05 and 2.0% of the weight (depending on the applied diphenols) to achieve obtain three or more trifunctional compounds, especially compounds with three or more than three phenolic hydroxyl groups. Some branched compounds with three or more than three phenolic hydroxyl groups are phloroglucin, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-hepten-2,4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptane, 1,3,5-tri-(4-hydroxyphenyl)-benzene, 1,1,1-tri-(4-hydroxyphenyl)-ethane, tri-(4-hydroxyphenyl)-phenylmethane, 2,2-bis-[4,4-bis-(4-hydroxyphenyl)-cyclohexyl]-propane, 2,4-bis-(4-hydroxyphenyl-isopropyl)-phenol, 2,6-bis-(2-hydroxy-5-methyl-benzyl)-4-METHYLPHENOL, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane, hexa-[4-(4-hydroxyphenyl-isopropyl)-phenyl]-ether of ochoterenai acid, Tetra-(4-hydroxyphenyl)-methane, Tetra-[4-(4-hydroxyphenyl-isopropyl)phenoxy]-methane and 1,4-bis-[4',4"-dihydroxydiphenyl)-methyl]-benzene. Some of the other trifunctional compounds are 2,4-dihydroxybenzoic acid, trimethine acid, cianuro and 3,3-bis-(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindol.

As agents of chain breakage known for the regulation of the molecular weight of the polycarbonate derivatives which serve monofunctional compounds in traditional concentrates. Suitable compounds are, for example, phenol, tert-butylphenol or other alkyl substituted phenols. To regulate the molecular weight is suitable, above all, a small amount of phenols by the formula (Ic)

where R represents a branched alkyl residue With8-and/or C9.

Preferable alkyl residue R is the proportion of CH3- protons between 47 and 89% and the proportion of CH and CH2- protons between 53 and 11%, also preferred is R in o - and/or p-position to the Oh group, and particularly preferably the upper boundary of the ortho-component of 20%. Agents circuits are used in General in amounts of from 0.5 to 10, preferably from 1.5 to 8% by weight, depending on the applied diphenols.

Preferably, the polycarbonate derivatives can be produced in accordance with the method of phase boundary (EUR. X. shell Chemistry and physics of polycarbonates", Reviews of polymers, volume IX, page 33 and the placenta., Interscience Publishers, 1964) per se known method.

Thus divinely by the formula (Ia) are dissolved in an aqueous alkaline phase. For the manufacture of copolycarbonates with other diphenolate apply a mixture of diphenols by the formula (Ia) and other divinely, for example by the formula (Ib). To regulate the molecular weight can be added agents, chain breakage such as fo the mule (Ic). Then made the conversion in the presence of an inert solvent preferably, the polycarbonates of the organic phase with phosgene by the method of condensation at the interface of two phases. The reaction temperature is between 0°C and 40°C.

Used, if necessary, splitters, preferably, from 0.05 to 2.0% by weight) can either be represented diphenolate in the aqueous alkaline phase or added to organic solvents in dissolved form to vosganian. Along with diphenolate (Ib) may also be used esters of mono - and/or bis-gloryhole acid, when they are added to organic solvents in dissolved form. The number of agents break the circuit, and splitters matches then the molar mass of the remnants of diphenolate by the formula (Ia) or, under certain conditions, according to the formula (Ib). When sharing esters harpalinae acid number of phosgene can, in a known manner, respectively, to decrease.

Suitable organic solvents for agents break the circuit, and, if necessary, for splitters and esters chloropurine acids are, for example, methylene chloride, chlorobenzene, primarily a mixture of methylene chloride and chlorobenzene. If necessary, used agents break the circuit and splitters can be dissolved in the same is rastvoritelyakh.

As the organic phase for preconceptionally at the interface of two phases is used, for example, methylene chloride, chlorobenzene and mixtures of methylene chloride and chlorobenzene.

As the aqueous alkaline phase is, for example, a NaOH solution. Manufacturer of polycarbonate derivatives by the method of phase boundary can usually be kataliziruetsa such catalysts as tertiary amines, especially tertiary aliphatic amines, such as tributylamine or triethylamine. The catalysts can be used in amounts from 0.05 to 10% by weight, based on the moles used diphenols. The catalysts may be added prior to foenisecii or within foenisecii or after foenisecii.

Polycarbonate derivatives can be produced according to a known method in a homogeneous phase, the so-called "method of pyridine, and also according to the method of transesterification in the melt using, for example, diphenylcarbonate instead of phosgene.

Polycarbonate derivatives can be linear or branched, they are homopolymerization or copolycarbonate based diphenols by the formula (Ia).

Due to any combination with other diphenolate, primarily diphenolate by the formula (Ib), properties of polycarbonates vary more favorable. is such copolycarbonate and polycarbonate derivatives are divinely by the formula (Ia) in quantities from 100% by weight to 2% by weight, preferably from 100% by mass to 10% by mass, and particularly in quantities from 100% by mass to 30% by weight, depending on the total number of units diphenol on 100% by mass.

A particularly preferred form of embodiment of the invention differs in that the polycarbonate derivative contains a copolymer primarily comprising monomer units M1 on the basis of the formula (Ib), especially Bisphenol a, and Monomeric units of M2-based gemenele disubstituted dihydroxyphenylethylamine, preferably 4,4'-(3,3,5-trimethylcyclohexane-I,1-diol)-diphenol, with the molar ratio M2/M1, preferably, greater than 0.3, and primarily more of 0.4, for example greater than 0.5. Because such copolymers unexpectedly found that the glass transition temperature after the first heating cycle Tg of lower than 150°C. during the second heating cycle can be increased, which can significantly improve the stability of the contained mixture.

Preferably, if the polycarbonate derivative has an average molecular weight (the average weight is at least 10000, preferably from 20000 to 300000.

In principle, the component can be essentially organic or aqueous. Essentially watery this means that up to 20% by weight of component b) can comprise solvents. Essentially organic means that component b can contain up to 5% by weight of water. Preferably, component b) contains or consists of aliphatic, cycloaliphatic and/or aromatic hydrocarbon, liquid organic ester, and/or mixtures of these substances. Preferably used organic solvents are halogen-free organic solvents. Are taken into account, above all, aliphatic, cycloaliphatic, aromatic hydrocarbons, such as mesothelin, 1,2,4-trimethylbenzene, cumene and solvent-naphtha, toluene, xylene, organic esters, such as methyl acetate, ethyl acetate, butyl acetate, methoxypropylacetate, ethyl-3-ethoxypropionate. Preferred are mesothelin, 1,2,4-trimethylbenzene, cumene and solvent-naphtha, toluene, xylene, esters of acetic acid, a complex of ethyl esters of acetic acid, methoxypropylacetate, ethyl-3-aticipation. Particularly preferred are: mesothelin (1,3,5-trimethylbenzene), 1,2,4-trimethylbenzene, cumene (2-phenylpropane), solvent-naphtha and ethyl-3-ethoxypropionate.

Suitable solvent mixtures include, for example: (a) from 0 to 10 wt.%, preferably from 1 to 5 wt.%, first of all, from 2 to 3 wt.% mesitylene, b) from 10 to 50 wt.%, preferably from 25 to 50 wt.%, first of all, from 30 to 40 wt.% 1-methoxy-2-propylacetate, C) from 0 to 20 wt.%, preferably from 1 to 20 wt.%, first of all, from 0 to 15 wt.% 1,2,trimethylbenzene, d) from 10 to 50 wt.%, preferably, from 25 to 50 wt.%, first of all, from 30 to 40 wt.% ethyl-3-ethoxypropionate, d) from 0 to 10 wt.%, preferably from 0.01 to 2 wt.%, first of all, from 0.05 to 0.5 wt.% cumene and from 0 to 80 wt.%, preferably from 1 to 40 wt.%, first of all, from 15 to 25 wt.% solvent-naphtha, the sum of components a) to e) always amounts to 100 wt.%.

Typically, the first polycarbonate layer and the second polycarbonate layer have a glass transition temperature Tg higher than 145°C., especially above 147°C.

Polycarbonate derivative has an average molecular weight (the average weight is at least 10000, preferably from 20000 to 300000.

The composition may be in the details contain: a) from 0.1 to 10% by weight, especially from 0.5 to 5% by weight of a binder with a polycarbonate derivative based on Genialnogo disubstituted dihydroxydiphenyl-cycloalkane, b) from 40 to 99.9% by weight, especially from 45 to 99.5% by weight of an organic solvent or mixture of solvents) from 0.1 to 6% by weight, especially from 0.5 to 4% by weight of the dye or mixture of solvents, d) from 0.001 to 6% by weight, especially from 0.1 up to 4% by weight of the functional material or a mixture of functional materials, e) from 0.1 to 30% by weight, especially from 1 to 20% by weight of additives and/or auxiliary substances or mixtures of such substances.

As component C), if the set includes a dye, in principle, considered any dye or mixture of dyes. Under the dye refers to all colorants. This means that it can go about coloring substances (review pigments gives "encyclopedia of industrial chemistry Ullman" / Ullmann''s Encyclopedia of Industrial Chemistry, electronic publication 2007, publisher Willey, Chapter "Dyes," / Dyes, General Survey), and pigments (for an overview of both organic and inorganic pigments gives encyclopedia of industrial chemistry Ullman, electronic publication 2007, publisher Willey, head Pigments, organic" or "Pigments, inorganic" / "Pigments, Organic" or "Pigments, Inorganic"). Dyes should be soluble or stable) dispergimini or Spiderwoman in the solvent of component b). Additionally, mainly, if the dye at temperatures of 160°C and is more sustainable, primarily svetoustoychiva, during the period of time for more than 5 minutes. It is also possible that the dye has been specified and reproduced color change in the treatment conditions and were selected accordingly. Pigments, along with temperature stability must be, first of all, the smallest particle size. In practice, inkjet printing, this means that the size of the particles should not exceed 1.0 μm, since otherwise the consequence b is to be clogging the printhead. As a rule, well established pigments, consisting of measured in the nano-range solid particles.

Coloring agents can be cationic, anionic, and neutral. Only as examples used in inkjet printing dyes can be named: brilliant black C.I. No. 28440, chromogenic black C.I. No. 14645, direct deep black E C.I. No. 30235, natural black salt C.I. No. 37245, natural black salt To C.I. No. 37190, Sudan black HB C.I. 26150, naphthol-black C.I. No. 20470, Bayscript® black liquid, C.I. basic black 11, C.I. basic blue 154, Cartasol® blue K-ZL fluid, Cartasol® blue K-RL liquid (C.I. basic blue 140), Cartasol® blue K5R liquid. In addition, suitable, for example, in the sale of dyes Hostafine® black TS liquid (sold by the company Clariant GmbH, Germany), Bayscript® black liquid (C.I. mixture, sold by Bayer AG, Germany), Cartasol® black MG liquid (C.I. basic black 11, a registered trademark of Clariant GmbH, Germany), Flexonylschwarz® PR 100 (E C.I. No. 30235, sold by the company Hoechst AG), Rhodamine B, Cartasol® orange K3 GL, Cartasol® yellow K4 GL, Cartasol® GL, or Cartasol® red K-3B. In addition, as a soluble dyes can be used anthraquinone-, azo-, chieftain-, coumarin-, Metin, perinon,and/or pyrazole - dyes, such as commercially available under the trademarks of Macrolex®. Other suitable dyes are described in IMS is nick literature encyclopedia of industrial chemistry Ullman electronic publication 2007, publisher Willey, head of the Dyes used in printing inks for inkjet printers. Soluble dyes lead to optimal integration in a matrix or binder printed layer. Dyes can be added either directly as a dye or pigment, or as a paste to the mixture of the coloring matter and pigment together with another binder. This additional binder may differ from those offered by the invention is a binder (for example, be a polyester), but must be chemically compatible with other components used according to the invention composition. If this paste is used as the dye, indicating the number of the component (b) refers to the dye, without taking into account other components of the paste. These other components of the paste should then be summarized in the composition of the components d). When using the so-called colored pigments in the colors of the scale cyan - Magenta - yellow and, preferably, also black soot possible color image type.

Component d) comprises a substance that, when applied technical AIDS are perceived by the human eye directly or through the use of appropriate detectors. Here are actually known in the art as suitable the materials (compare also Renesse, Optical document security / Renesse, Optical document security, 3rd edition, Artech House, 2005), which are used as the protection of valuable documents and/or protected against forgery. These include fluorescent substances (dyes or pigments, organic or inorganic), such as, for example, photoluminous, electroluminophores, Antistax-phosphor, a fluorophore, and magnetoterapia, photoacoustic addressed or piezoelectric materials. In addition, can be used Raman-active or Raman-enhancing material, and a so-called bar code materials. Here also as the preferred criteria are either soluble in the component (b), or in pigmented systems, the size of the particles <1 μm, and thermal stability at temperatures of >160°C in the sense of accomplishments relative to the component). Functional materials can be added directly or through the paste that is a mixture with another binding agent, which then is an integral part of component d), or used according to the invention the binder component a).

Component d) contains traditionally located in the ink for inkjet printing substances, such as anti-foam agents, thickeners, wetting agents, surfactants, dilute the Lee, desiccants, catalysts, light stabilizers, preservatives, biocides, surfactants, organic polymers to adjust the viscosity, buffer systems, etc. as thickeners are considered normal in this area of salt-thickeners. Their example is sodium lactate. As biocides are taken into account all trade preservatives, which are used for inks. Their examples are Proxel®GXL and Parmetol®A26. As surface-active substances are taken into account all industrial (commercially available) surfactants, which are used for inks. Preferred are amphoteric or noniongenetical surfactants. Of course, you can also use special anionic and cationic surfactants that do not change the properties of the dye. Examples of appropriate surfactants are the betaines, ethoxylated diol, etc. Examples are line products Surfynol®, Tergitol®. The amount of surfactants is selected, for example, proceeding from the condition that the surface tension of the ink is in the range from 10 to 60 mn/m, for example 25 to 45 mn/m, measured at 25°C. Can be set buffer system, which stabilizes the pH value in the range from 2.5 to 8.5, before the e from 5 to 8. Suitable buffer systems are lithium acetate, borate buffer, triethanolamine or acetic acid/sodium acetate. The buffer system is considered, first of all, if, in fact watery component b). To adjust the viscosity of the ink (when known conditions, water-soluble) can be provided by the polymers. Here the calculation includes all polymers suitable for standard ink compositions. Examples are water-soluble starches, primarily with an average molecular weight of from 3000 to 7000, polivinilpirolidon, first of all with an average molecular weight from 25,000 to 250,000, polyvinylalcohol, first of all with an average molecular weight of from 10,000 to 20,000, xanthan gum, carboxy methyl cellulose, ethylene oxide/propylene oxide-block copolymers, especially with an average molecular weight of from 1000 to 8000.

The example mentioned blockcopolymer is a line of products Pluronic®. The share of biocide to the total volume of ink can be in the range from 0 to 0.5% by weight, preferably from 0.1 to 0.3% by weight. The proportion of surfactants to the total volume of ink can be in the range from 0 to 0.2% by weight. The proportion of the thickening agent to the total amount of ink can be from 0 to 1% by weight, preferably from 0.1 to 0.5% by mass.

The supporting means also includes other components, such the AK, for example, acetic acid, formic acid or n-methyl-pyrolidone or other polymers of the applied mortar pigments or ink paste.

Regarding substances that are suitable as component d), optionally as an example, reference is made to Encyclopedia of industrial chemistry Ullman, electronic publication 2007, publisher Willey, head of the "Additive colors".

In addition, the invention relates to a method of manufacturing a composite of at least one first polymer layer, and, optionally, a second polymer layer, in each case consisting of a polycarbonate polymer based on Bisphenol a, the first polymer layer is a layer for inkjet printing with the following stages of the method: a) at least at the site of the first polymer layer is applied a layer for inkjet printing of the applied according to the invention composition, b) optionally, a layer for inkjet printing is subjected to drying, C) optionally, after step a) or step b on the first polymer layer impose, covering layer for inkjet printing, the second polymer layer, and the first polymer layer and second polymer layer laminated to each other under pressure at a temperature of from 120°C to 230°C and within a specified period of time.

In other words, the proposed composite may be the only one polymer layer and caused by used according to the invention the composition of the printed layer, and may also include another polymer layer, optionally in further combination with additional layers. Thus, for example, it is possible that the printed layer was disposed as an upper layer within the composite (for example, additional layers). Also printed layer can be napechatan directly and without additional coating is made in the form of a coating film of the polymer layer.

Layer for inkjet printing can be on the entire surface of the first polymer layer. Mostly, however, the layer for inkjet printing is only on the surface area of the first polymer layer.

Specific pressure (pressure directly on the workpiece in step C) is generally in the range from 1 bar to 10 bar, particularly in the range from 3 bar to 7 bar. Preferably, the temperature in step C) is in the range from 140°C to 200°C, especially in the range from 150°C to 180°C. the Duration of step C) may be in the range from 0.5 sec to 120 sec, primarily, from 5 sec to 60 sec.

At the stage b) drying may be conducted at a temperature in the range from 20°C to 120°C, especially from 20°C to 80°C, preferably from 20°C to 60°C for at least 1 second, preferably from 5 seconds to 6000 seconds.

The first polycarbonate layer and the second polycarbonate layer can independently the t other to have a glass transition temperature Tg of more than 145°C.

The thickness of the first polycarbonate layer and the second polycarbonate layer may be the same or different in the range of 10 to 1000 μm, especially 20 to 200 microns.

The thickness of the layer for inkjet printing in directions perpendicular to the main surface of the polycarbonate layer may, before or after drying to be in the range from 0.01 to 10 μm, particularly from 0.05 to 5 μm, preferably from 0.02 to 1 μm.

The subject of invention is a composite obtained by the proposed method. Such a composite, usually contains at least a first polycarbonate layer and the second polycarbonate layer and located between the first polycarbonate layer and the second polycarbonate layer is a printed layer of a proposed according to the invention composition.

The proposed method of manufacturing a composite material can be used for making protected against forgery and/or valuable document, with optional simultaneously during manufacture, prior to fabrication or after fabrication of the composite first polycarbonate layer and/or the second polycarbonate layer interconnect directly or indirectly with at least one further layer, for example, the carrier layer.

Among protected against forgery and/or valuable document, for instance, can be named: is oseverenie personality, passports, identification cards, certificates, access control, visas, tax stamps, tickets, driver's license, the documents of the vehicle, banknotes, cheques, postage marks, credit card, any card with an integrated chip and self-adhesive labels (for example for protection products). Such documents with security features and/or valuable documents, typically have at least one substrate (the substrate), a printed layer, and optionally a transparent cover layer. The substrate and the covering layer can, in turn, be composed of a larger number of layers. The substrate is a bearing structure to which is applied a printed layer with information, images, designs, etc. as materials for the substrate can be considered all commonly understood in the field of materials on paper and/or organic polymer-based. Such is protected from a fake document and/or valuable document includes within the overall composite layers proposed according to the invention the composite. Along with the proposed composite can contain at least one (additional) printed layer which can be deposited on the external surface of the joint or combined with additional composite layer.

Finally, the invention relates to tamper d is the document and/or valuable document, manufactured thereby, or containing the proposed connection.

However, the invention can be used in other technological areas. So, by spraying the film can be formed of wear resistant (abrasion resistant) artwork produced by pressure die casting parts. According to the prior art on the polycarbonate film when it is applied screen printing, they are plastically deformed (for example, deep drawing)are placed in the mold for injection molding, and spray-applied thermoplastic plastic. So are manufactured, for example, in the case of mobile phones or decorative housing. Multicolor decorations that make the production of several printing forms/screen grids and, therefore, are cost-effective only for parties with the appropriate number. However, using the applied ink according to the invention possible piece manufacture or unique motives, and thus can be manufactured, for example, individual, speed case for mobile phones (for example, with photo) or individual gauges (for example, with the initials of the owner).

Consequently, the invention relates also to a method of manufacturing a composite material with at least one polymer is a layer and obtained by injection molding a shaped part made of a polymeric material, while between the polymer layer and the fitting is a layer for inkjet printing, with the following stages of the method: a) at least a section of the polymer layer is applied a layer for inkjet printing of the applied according to the invention composition, b) optionally, a layer for inkjet printing is subjected to drying, then, in step a) or step b) polymer layer is placed in a mold for injection molding (if necessary after plastic deformation of the polymer layer printed for approval with the walls of the mold for casting under pressure) with directed inward layer for inkjet printing, g) in the mold for injection molding inject polymeric material at a temperature of at least 60°C, and d) composite after cooling to a temperature at least 20°C lower than the temperature in step d) is removed from the mold for injection molding.

Preferably, the polymeric layer may be a polycarbonate layer on the basis of Bisphenol A. as polymeric materials, in principle, the calculation includes all polymers commonly used in the field of plastic molding under pressure.

The temperature at the step d) may be in the range from 80°C to 200°C, before the package is in the range from 100°C to 180°C. The temperature at the step d) may be at least 40°C. lower than the temperature in step d).

In principle, everything else is provided in connection with composite protected against forgery and/or valuable documents are similar. Therefore, the invention also includes a composite containing at least one polycarbonate layer and obtained by molding the fitting and located between the polycarbonate layer and obtained by molding the fitting layer for inkjet printing used according to the invention composition.

Further, the invention is more particularly described on the basis of non-limiting examples of execution. Shown:

Figure 1: test image square printing, and

Figure 2: detail of the portrait of the person obtained by the proposed method.

Example 1: Preparation used according to the invention the polycarbonate derivative

Example 1.1: Production of the first polycarbonate derivative

KZT 205.7 g (0.90 mol) of Bisphenol a (2,2-bis-(4-hydroxyphenyl)-propane, of 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 are dissolved in an inert atmosphere with stirring. Then added a solution of 1.88 g of phenol in 2500 ml of methylene chloride. In a well-stirred solution at pH 13 to 14 and 21 to 25°C is injected 98 g (2 mol) of phosgene. After this is added 1 ml of ethylpiperidine and mix for a further 45 minutes. The aqueous phase without content bisphenolate separated, the organic phase after oxidation using phosphoric acid, washed with water until neutral and freed from solvent.

Polycarbonate derivative showed a relative viscosity of a solution equal to 1,255, the glass transition Temperature was determined in the amount of 157°C (DSC).

Example 1.2: the Making of the second polycarbonate derivative

Analogously to example 1, a mixture consisting of 181,4 g (0,79 mol) of Bisphenol a and 63.7 g (0.21 mol) of 1,1-bis-(4-hydroxyphenyl)-3,3,5-themeteorological, was turned into a polycarbonate derivative.

Polycarbonate derivative showed the viscosity of the solution is equal to 1,263. The glass transition temperature was determined in the amount of 167°C (DSC).

Example 1.3: the Making of the third polycarbonate derivative

Analogously to example 1, a mixture consisting of of 149.0 g (of 0.65 mol) of Bisphenol a (2,2-bis-(4-hydroxyphenyl)-propane and 107,9 g (0.35 mol) of 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, was turned into a polycarbonate derivative.

Polycarbonate derivative showed the viscosity of the solution is equal to 1,263. The glass transition temperature was determined in the amount of 183°C (DSC).

Example 1.4: Making fourth polycarbonate derivative

Analogously to example 1, the mixture is, consisting of 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, was turned into a polycarbonate derivative.

Polycarbonate derivative showed the viscosity of the solution, equal 1,251. The glass transition temperature was determined in the amount of 204°C (DSC).

Example 1.5: Making fifth polycarbonate derivative

As in example 1, 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, was turned into a polycarbonate derivative.

Polycarbonate derivative showed the viscosity of the solution is equal to 1,248. The glass transition temperature was determined in the amount of 216°C (DSC).

Example 2: Production of liquid compositions suitable for ink for inkjet printing

The liquid composition was made from the mass of 17.5 parts of polycarbonate derivative from example 1.3 and 82.5 mass parts of a solvent mixture in accordance with table I.

Table 1
Mesitylene2,4
1-methoxy-2-propylacetate34,95
1,2,4-trimethylbenzene10,75
Ethyl-3-ethoxypropionate 33,35
The cumene0,105
Solvent-naphthaof 18.45

There was obtained a colorless highly viscous solution with a viscosity at room temperature of 800 mPas.

Example 3: Production of the first to be used according to the invention inks for inkjet printing

In a wide-mouthed glass with thread with a capacity of 50 ml using a magnetic stirrer were homogenized 4 g of the solution of the polycarbonate from example 2 and 30 g of a solvent mixture of example 2. There was obtained a colorless, low viscosity solution with the viscosity of the solution at room temperature 1,67 mPas.

Surface tension of these basic ink was determined using the measuring system OEG Surftens method for hanging drops as 21,4±1,9 mn/m

Adding pigment or coloring matter was not implemented, because these inks are served only for use under a test pressure of example 6.

Example 4: Production of the second, used according to the invention inks for inkjet printing

Analogously to example 3, 10 g of the solution of the polycarbonate from example 2 and 32.5 g of a mixture solvent of example 2 were homogenized using a magnetic stirrer (4% polycarbonate solution). There was obtained a colorless, low viscosity solution of 20°C viscosity 5,02 mPas. Here doba is of pigment or coloring matter was not done because these inks are served only for use in a test pressure of example 7.

Example 5: Production of a third, used according to the invention inks for inkjet printing

Was made of polycarbonate solution according to example 4, and optionally mixed with about 2% pigment Black 28. Received the ink, by which on polycarbonate films may be printed black and white images, which additionally provides a link to the example 8.

Example 6: droplet Size at a pressure of ink according to example 3

The solution from example 3 through the filter was transferred to the printer cartridge was used to print on an inkjet printer FUJIFILM-Dimatix DMP 2800 with a variation of different print settings. When used printer we are talking about the so-called drip-pulse (Drop-On-Demand) system, in which the formation of drops occurs through a piezoelectric printhead. The printer DMP 2800 has a stroboscopic image transmission by means of which it is possible to observe the formation and flight drops. The printed material was dried at 100°C for 30 minutes. As shown in table 1, depending on the substrate can be different droplet sizes.

Table 1
SubstrateGlassPolycarbonate (smooth)Vilanova paper
Separate drop~74 microns~85 µm~100 mm

On absorbent substrates drops in accordance with the expectation of filling more than on non-absorbent substrates, such as glass or plastic.

Example 7 determination of the thickness of the layer for inkjet printing

The ink according to example 4 were printed on a glass substrate. When this so-called distance between the drops (step, see also figure 1) ranged from 10 to 45 μm. The prints were again subjected to drying at 100°C for 30 minutes. Then, measurements were taken of the thickness of the layer (Arithmetic Step Height=ASH) using a profilometer (Dektak 6M,12.5 μm Stylus), the results of which are summarized in table 2.

Table 2
StepASH [nm]
10 µm685
30 µm100
45 microns27

Already due to the distance between the drops, the thickness of the layer which can be adjusted in a wide range.

Example 8 Production of images and check the optical quality after lamination

The ink of example 5 was printed portrait of a man on film Macrofol® 4-4. Made so the portrait was laminated together with a clear 6-2 Macrofol® films at temperatures >180°C, pressures >5 bar and time >10 min in a composite thickness of about 800 μm. However, the observations were performed by the method of light microscopy before and after lamination to ensure that it was possible to make conclusions about the sharpness of the individual pixels on the edges of the image. The results are shown in figure 2.

The figure 2 shows the top color prints (top)and the same prints from below, and only after conversion to black and white. To the left is seen a detailed picture is obtained in accordance with the invention, a layer for inkjet print-to-lamination. The right shows the same detailed picture after lamination. It is seen that the pattern of halftone dots remains almost the same resolution also and after lamination. Horizontal lines are obtained from overlapping areas of the individual jet nozzles of the print head and, therefore, are not relevant to the proposed ink.

Optical examination of the composite no longer gave no discernible at the phase boundaries. The composite showed himself as a monolithic block, eliminate inim way resistant to delaminating.

1. The use of a composition containing:
a) from 0.1 to 20% by weight of a binder comprising a polycarbonate derivative based on gemenele disubstituted dihydroxydiphenyl-cycloalkane,
b) from 30 to 99.9% by weight of the solvent or solvent mixture,
C) from 0 to 10% by weight, referred to the dry weight, of the dye or mixture of dyes,
g) from 0 to 10% by weight of the functional material or a mixture of functional materials,
d) from 0 to 30% by weight of additives and/or auxiliary substances, or mixtures of such substances,
the sum of components a) to d) is always 100% by weight, while the polycarbonate derivative contains functional units carbonates according to the formula (I),

where R1and R2independently of one another represent hydrogen, halogen, preferably chlorine or bromine, With1-C8-alkyl, C5-C6-cycloalkyl,6-C10-aryl, preferably phenyl, and C7-C12-aralkyl, preferably, phenyl-C1-C4-alkyl, especially benzyl,
m is an integer from 4 to 7, preferably 4 or 5,
R3and R4individually selectable for each X, independently from each other hydrogen or C1-C6-alkyl,
X is carbon, and
n denotes a whole number greater than 20,
with the proviso that at least one atom X, R and R4simultaneously denote C1-C6-alkyl,
as inks for inkjet printing.

2. The use according to claim 1, the derivative of polycarbonate has an average molecular weight (the average weight is at least 10000, preferably from 20000 to 300000.

3. The use according to claim 1, where 1 or 2 atoms X, preferably only one atom X, R3and R4at the same time are C1-C6-alkilani.

4. The use according to claim 1, with R3and R4are metelli.

5. The use according to claim 1, in this case the atoms X in alpha-position to the diphenyl-substituted atom With (C1) is not disonesty alkilani.

6. The use according to claim 1, in this case the atoms X in beta-position to the diphenyl-substituted atom With (C1) disonesty alkilani.

7. The use according to claim 1, with m=4 or 5.

8. The use according to claim 1, with a polycarbonate derivative is formed on the basis of
4,4'-(3,3,5-trimethylcyclohexane-1,1-diol)-diphenol, 4,4'-(3,3-dimethylcyclohexane-1,1-diol)-diphenol or 4,4'-(2,4,4-trimethylcyclopentanone-1,1-diol)-diphenol.

9. The use according to claim 1, with a polycarbonate derivative contains copolymers, primarily consisting of monomer units M1 on the basis of the formula (Ib), for example on the basis of Bisphenol a and monomer units of M2-based gemenele disubstituted dihydroxydiphenyl-cycloalkane, preferably 4,4'-(3,3,5-trimethylcyclohex exan-1,1-diol)-diphenol, when this molar ratio M2/M1, more preferably of 0.3, especially more and 0.40, preferably more than 0.50.

10. The use according to claim 1, the component b) is halogen-free.

11. The use according to claim 1, the component (b) consists of aliphatic, cycloaliphatic and/or aromatic hydrocarbon, liquid organic ester, and/or mixtures of these substances.

12. The application of claim 11, the hydrocarbon and/or an organic ester selected from the group mesitylene, 1,2,4-trimethylbenzene, cumene, solvent-naphtha, toluene, xylene, methyl acetate, ethyl acetate, butyl acetate, methoxypropylacetate, ethyl-3-ethoxypropionate".

13. The application indicated in paragraph 12, the component (b) consists of:
L1) from 0 to 10% by weight, preferably from 1 to 5% by weight, especially from 2 to 3% by weight, mesitylene,
L2) from 10 to 50% by weight, preferably from 25 to 50% by weight, especially 30 to 40 mass% 1-methoxy-2-propylacetate,
L3) from 0 to 20% by weight, preferably from 1 to 20% by weight, especially from 7 to 15% by weight, 1,2,4-trimethylbenzene,
L4) from 10 to 50% by weight, preferably from 25 to 50% by weight, especially from 30 to 40% by weight, ethyl-3-ethoxypropionate,
L5) from 0 to 10% by weight, preferably from 0.01 to 2% by weight, especially from 0.05 to 0.5% by weight, cumene, and
L6) from 0 to 80% by weight, preferably from 1 to 40% by weight, especially from 15 to 25% by weight, with Levent-nafta,
the sum of the components L1 to L6 is constantly 100%.

14. The use according to claim 1, the composition contains:
a) from 0.1 to 10% by weight, especially from 0.5 to 5% by weight, a binder with a polycarbonate derivative based on gemenele disubstituted dihydroxydiphenyl-cycloalkane,
b) from 40 to 99.9% by weight, especially from 45 to 99.5% by weight, of an organic solvent or mixture of solvents,
C) from 0.1 to 6% by weight, especially from 0.5 to 4% by weight, of the dye or mixture of dyes,
d) from 0.001 to 6% by weight, especially from 0.1 to 4% by weight, functional material, or a mixture of functional materials,
d) from 0.1 to 30% by weight, especially from 1 to 20% by weight, of additives and/or auxiliary substances, or mixtures of such substances.

15. A method of manufacturing a composite of at least one first polymer layer, and, optionally, the second polymer layer, in each case from a polycarbonate polymer based on Bisphenol a, the first polymer layer is a layer for inkjet printing, with the following stages of the method:
at least on the site of the first polymer layer is applied a layer for inkjet printing of compositions according to claims 1 to 14,
b) optionally, a layer for inkjet printing is being dried,
C) optionally, after step a) or step b) on the first polymer layer impose the, covering layer for inkjet printing, the second polymer layer, and the first polymer layer and second polymer layer laminated to each other under pressure at a temperature of from 120°C to 230°C and within a specified period of time.

16. The method according to clause 15, the temperature in step C) is in the range from 140°C to 200°C, especially in the range from 150°C to 180°C.

17. The method according to clause 15, the first polymer layer and second polymer layer have a glass transition temperature Tg of more than 145°C.

18. The method according to clause 15, the thickness of the first polycarbonate layer and the second polycarbonate layer is up to 1000 μm, especially 20 to 200 microns.

19. The method according to clause 15, the thickness of the layer for inkjet printing, measured in directions perpendicular to the main surface of the polycarbonate layer is in the range from 0.01 to 10 μm, particularly from 0.05 to 5 μm.

20. The composite obtained by the method according to one of PP-19.

21. The composite containing at least the first polycarbonate layer and located on the first polycarbonate layer for inkjet printing of the composition according to one of claims 1 to 14, with optional opposite the first polycarbonate layer side of the printing layer may be located a second polycarbonate layer.

22. Application of the method according to one of PP-19 for the manufacture of counterfeit dock the cops and/or valuable documents, when this optional simultaneously with the manufacturer, to manufacture or after manufacture of the composite first polycarbonate layer and/or the second polycarbonate layer interconnect directly or indirectly with at least one further layer, for example bearing layer.

23. Protected from a fake document and/or valuable document, obtained by p.22.

24. Protected from a fake document and/or valuable document containing composite according to claim 20 or 21.

25. A method of manufacturing a composite material with at least one polymer layer, and also obtained by molding a shaped part made of a polymeric material, while between the polymer layer and the fitting is a layer for inkjet printing, with the following stages of the method:
a) at least a section of the polymer layer is applied a layer for inkjet printing of compositions according to claims 1 to 14,
b) optionally, a layer for inkjet printing is being dried,
C) then, in step a) or step b) polymer layer is placed in a mold for casting under pressure directed inward layer for inkjet printing,
g) in the mold for injection molding inject polymeric material at a temperature of at least 60°C, and
d) composite after cooling to a temperature at least 20°C lower than the temperature in step d) is removed from the mold for casting under pressure is m

26. The method according A.25, the temperature in step d) is in the range from 80°C to 200°C, especially in the range from 100°C to 180°C, and/or the temperature in step d) is at least 40°C below the temperature of step d).

27. The method according to one of p or 26, while the polycarbonate layer has a glass transition temperature Tg higher than 145°C., especially above 147°C.

28. The method according A.25, the thickness of the polycarbonate layer is in the range from 10 to 1000 μm, especially 20 to 200 microns.

29. The method according A.25, the thickness of the layer for inkjet printing, measured in the direction perpendicular to the main surface of the polycarbonate layer is in the range from 0.01 to 10 μm, particularly from 0.05 to 5 μm.

30. The composite obtained by the method according to one of PP-29.

31. The composite containing at least one polycarbonate layer and obtained by molding the fitting and located between the polycarbonate layer and obtained by molding the fitting layer for inkjet printing of the composition according to one of claims 1 to 14.



 

Same patents:

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.

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3 cl, 1 tbl, 9 ex

FIELD: organic chemistry, chemical technology.

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FIELD: chemistry.

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,

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.

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16 cl, 1 dwg, 4 tbl

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16 cl, 2 dwg, 2 tbl, 2 ex

FIELD: chemistry.

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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: dyes.

SUBSTANCE: invention relates typography dyes, in particular, to dye for deep printing. Invention describes dye for deep printing comprising the first binding agent chosen from group of water-soluble or water-diluted acrylate oligomers, photoinitiating agent and, optionally, a monomer as the second binding agent chosen from group consisting of water-soluble or water-diluted monomers of polyethylene diacrylates or polyethoxylated triacrylates used for correction of the composition dye viscosity value. Dye can comprise additives, such as pigments, filling agents, photosensitizing agents, photostabilizing agents and special pigments. Dyes shows viscosity value from 7 to 60 Pa . s at temperature 40°C and dispersed completely in aqueous washing off solution with sodium hydroxide in the concentration from 0 to 0.5 wt.-%. Dyes possesses the excellent capacity for paint removing and it is can be precipitated from the indicated washing off solution.

EFFECT: improved and valuable properties of dye.

28 cl, 9 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

FIELD: printing industry.

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

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

14 cl, 6 tbl, 6 ex

FIELD: printing industry.

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

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

13 cl, 7 tbl, 7 ex

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