RU2640521C1 - Colourful composition, multilayer polycarbonate composite and method of its manufacture - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: colourful composition is described, containing, wt %: a binder comprising a polycarbonate derivative based on geminally disubstituted dihydroxyphenylalanine - 0.1-10.0; dye or mixture of dyes - 0.0-5.0; a functional material or a mixture of functional materials - 0.0-5.0; excipients - 0.0-10.0; a solvent or a mixture of solvents - to 100%. The polycarbonate derivative has luminescent properties and contains functional structural units of carbonates connected statistically or blockwise according to the formula

,

where R₁ - hydrogen or alkyl (C₁-C₃); R₂ - alkyl (C₅-C₈), cycloalkyl (C₅-C₆), arylalkyl (C₇-C₁₂); R₃ - fluorophore; n, m, k are integers denoting the number of the functional structural units in the molecule of the polycarbonate derivative. The ratio n/(n+m+k) is from 0.60 to 0.80; the ratio m/(n+m+k) is from 0.15 to 0.30; the ratio k/(n+m+k) is from 0.05 to 0.10. A multilayer polycarbonate composite and a method for manufacturing a multilayer polycarbonate composite are also disclosed.

EFFECT: method is developed for the production of anti-fake and lamination-resistant polycarbonate multilayer composites.

25 cl, 14 ex

Description

The invention relates to protected ink compositions for printing on plastic materials, in particular on polycarbonate materials. The invention also relates to colorful compositions containing a binder comprising a polycarbonate derivative (copolymer) based on geminally substituted dihydroxyphenylalkane. In this case, the polycarbonate derivative contains three types of functional structural units of carbonates, connected statistically or in blocks, which perform the following functions:

- geminally disubstituted dihydroxyphenylalkane increases the solubility of the polymer in non-halogenated solvents;

- bisphenol A reduces the glass transition temperature of the polymer and increases the affinity for polycarbonates based on pure (only) bisphenol A;

- the fluorophore imparts luminescent (and possibly chromophore) properties to the polymer molecule for additional protection against counterfeiting.

The invention also relates to a multilayer polycarbonate composite, such as a plastic card, identification document or valuable document, characterized in that it contains at least one ink layer, occupying from 1% to 99% of the frontal projection area of the composite and made with a colorful composition. A method of manufacturing a multilayer polycarbonate composite includes the step of applying a colorful composition to at least one of the layers prior to the step of laminating the layers into a single monolithic composite.

The process of manufacturing plastic cards usually consists of assembling functional polymer layers in various ways (continuous, semi-continuous and cyclic), laminating, cutting down the finished cards and checking the quality of the cards made and / or at each stage of manufacture.

With the continuous assembly method (from roll to roll), all polymer layers are sent parallel to each other and move at the same speed, while at the very beginning the layers are precisely registered, which is controlled before lamination. Subsequent lamination of layers located exactly one above the other is a fast, efficient and technologically advanced method.

During sheet lamination (cyclic assembly), individual sheets of polymer layers containing several documents are collected in a lamination package and placed in a laminator. This assembly method may include quality control up to each individual sheet.

The semi-continuous assembly method involves bringing all the layers of a plastic card together in one place, with individual polymer layers being fed both from a roll and in the form of sheets. This method also provides the ability to feed sheets of individual layers in a direction perpendicular to the movement of the main fabric.

Lamination of polymer layers (combining them with each other or combining into a monolithic composite) is usually carried out in special devices (laminators) at temperatures from 140 ° C to 270 ° C and at a compression pressure of the layers from 10 to 200 bar. Preferred are temperatures from 140 ° C to 200 ° C and pressures from 50 to 130 bar.

In the manufacture of monolithic composites from polycarbonate polymer layers, the temperature should be higher than the glass transition temperature of polycarbonate (147 ° C for a bisphenol A-based homopolymer), but below its melting temperature (230 ° C), and the pressure and exposure time should be strictly maintained for prevent deformation of polymer layers / plastic cards. The resulting monolithic composite should not contain layers having a low affinity for polycarbonate, to prevent their separation.

Some types of lamination include joining layers of polymer materials of various nature (not a monolithic composite), while bonding is carried out by means of hot-melt adhesive, chemical reaction or UV polymerization. In the case of using hot-melt adhesive, the polymer layers can be easily delaminated without serious damage when heated to the glass transition temperature of hot-melt adhesive, which is usually less than 100 ° C, and when using chemical or UV polymerization, it is necessary to apply liquid over the entire area between the layers, which is significantly complicates the process and increases the amount of marriage.

Thus, the manufacture of monolithic composites from homogeneous polymeric materials is the most protected from the delamination and subsequent manipulation of plastic card data by the manufacturing method.

The manufacture of plastic cards also provides for the inclusion of information in them, including visually recognizable personal information about the owner (photo, name, date of birth, passport number, etc.).

Various methods are known for applying information to a fake-protected plastic document using a laser (DE 2907004, DE 3151407 and EP 0219011). Using such methods, information can be applied to the surface of the plastic card or inside it, however, despite the high degree of protection against delamination of plastic cards, these methods are limited to one color - black.

The known technologies are “LASINK” (“Oberthur Technologies”) and “Sealys Color in Polycarbonate” (“Gemalto”), which involve the use of laser radiation to obtain color images in polycarbonate cards, however, this technology requires high precision register and focus the laser beam.

There are various methods of manufacturing counterfeit plastic cards (US 6685312, US 6932527, US 6979141, US 7037013, US 6022429 and US 6264296), while the information (images) is applied by inkjet printing, and then, if necessary, the printed layer is protected with a protective varnish or a protective film to protect against mechanical and / or chemical damage or manipulation. However, in all these cases, the printed layer containing personal information is close to the outer surface of the card, which does not provide the degree of reliability from data manipulation as in the case of using monolithic polycarbonate composites, when the printed layer can be located at a sufficient depth.

In addition, most commercially available inkjet inks have a very low affinity for the printing layer obtained by lamination to polycarbonate, which makes easy delamination in the printing area possible. The most promising solvent inks, which are well fixed on the surface of polycarbonate layers and other polymers due to partial dissolution (etching) or swelling of the substrate, however, during lamination, the top of the printed layer does not form any compound with polycarbonate during lamination.

The most promising approach to the use of inkjet solvent inks for obtaining color images in plastic cards (especially polycarbonate) is the use of a polycarbonate-based binder having a high affinity for polymer layers.

Patents of Bayer and Bundesdruckerei EP 0688839, RU 2497858, RU 2474498, RU 2481957, RU 2492057, RU 2497684 and RU 2526680 are disclosed, which describe the use of a polycarbonate derivative (copolymer) based on gemini disubstituted dihydroxyphenyl cyclo non-halogenated solvents for the manufacture of multilayer polymer composites. As examples in these documents, the use of copolycarbonates based on bisphenol A and bisphenol TMS as a binder in ink for color inkjet printing and inks for screen printing is given. The polymer layers formed by such copolymers have a high affinity for bisphenol A-based polycarbonate layers and, after lamination, form a monolithic composite with them, which has a high degree of protection against delamination. However, the use of such ink provides for the presence of special expensive equipment (inkjet printer) designed for this ink. In addition, the solvents used in such inks are carcinogenic, which can adversely affect the health of staff. The presence of pigments, including luminescent pigments used as protective elements, causes a high content of polycarbonate polymer in the ink formulation.

It is known that any foreign (not having an affinity for polycarbonate) components of the printing layer formed by inkjet solvent inks (binder, pigments, dispersants, wetting agents, plasticizers, etc.) only reduce the adhesive force of the polymer layers of the plastic card during lamination, preventing the formation of a monolithic compound.

The closest analogue of the invention is a method of manufacturing a polycarbonate multilayer composite (patent RU 2497858), in which a polycarbonate derivative (copolymer) based on geminally disubstituted dihydroxyphenylcycloalkane is used as a binder for ink.

The disadvantages of this method are too high the glass transition temperature of the copolymers, which can lead to an increase in the lamination temperature, as well as a rather high content of the binder in the composition of the ink to level the effects of colorful (and / or protective luminescent) pigments and functional materials (dispersants, wetting agents, etc.) the adhesion of the polymer layers of the plastic card.

The technical problem solved by the invention is the development of a new method of manufacturing protected from falsification and resistant to delamination of polycarbonate multilayer composites (plastic cards) containing color images, including personal information (photo, name, date of birth, etc.), devoid of the disadvantages described above.

The technical result achieved by the implementation of the invention is to increase the degree of security and simplify the process of manufacturing plastic cards through the use of a colorful composition containing a polycarbonate derivative (copolymer) based on geminally substituted dihydroxyphenylalkane, bisphenol A and fluorophore.

Disclosure of invention

To solve this problem, it is proposed to use a colorful composition containing a polycarbonate derivative (copolymer) based on heminally disubstituted dihydroxyphenylalkane, bisphenol A and fluorophore (as one of the protection elements), for applying images to polymer layers, from which a plastic card is subsequently made.

The use of a luminescent (and possibly dyed) polymer eliminates the need for dispersion of protective luminescent (and / or colorful) pigments and / or reduces the number of such pigments (as well as functional materials necessary for dispersing - dispersants, wetting agents and other stabilizers) in the final formulation of the composition. This increases the affinity of the composition (after removal, evaporation, drying of the solvent) to polymeric materials during lamination and simplifies the process of its manufacture.

The invention also relates to a method of using a colorful composition - the manufacture of tamper-resistant plastic cards (especially polycarbonate), which may contain color images.

As noted above, the most promising way to obtain color images is to use inkjet printing with solvent inks containing a polymer having a high affinity for polycarbonate.

Such a polymer, used as a binder in inkjet solvent ink, must have the following properties:

- high affinity for polycarbonates based on bisphenol A, of which the polymer layers consist;

- solubility in non-halogenated solvents (to prevent excessive warpage of the substrate and clogging of the nozzles of the print head) that do not have carcinogenic properties;

- low glass transition temperature, first of all, lower or equal to the lamination temperature, but higher than the glass transition temperature of the layers, to prevent delamination at temperatures at which deformation or damage to the base layers does not occur;

- molecular weight for good print quality and film-forming properties, including during lamination (more than 10,000);

- luminescent (and possibly chromophore) properties (to reduce the number of protective luminescent and / or coloring, as well as auxiliary components (dispersants, wetting agents and other stabilizers), which increases the affinity of the paint layer to polycarbonate).

From literary sources (Schnell G. Chemistry and Physics of Polycarbonates. Translation from English. - M .: Chemistry, 1967; Smirnova OV, Erofeeva SB. Polycarbonates. - M .: Chemistry, 1975) it is known that the solubility of aromatic polycarboants depends, first of all, on the degree of crystallinity and the nature of the initial dioxo compounds. Most polycarbonates are soluble in chlorinated hydrocarbons, pyridine, dimethylformamide, cyclohexanone and other solvents. This is true for polycarbonates with a minimum packing density, as a result of which the energy of intermolecular interaction is not high, which leads to dissolution under mild conditions in solvents of various nature. The solubility is much worse in those conditions when the macromolecules are packed tightly due to the presence of flexible units or there is a strong intermolecular interaction.

The presence of substituents on the central carbon atom of bis- (4-hydroxyphenyl) methane derivatives or in aromatic radicals usually increases the solubility; in mixed polycarbonates it is higher than in the corresponding homopolycarbonates.

The best solubility of aromatic polycarbonates is demonstrated by compounds containing bulky substituents (especially containing rings) at the central carbon atom, which leads to the formation of amorphous polymers.

It is known to use bisphenols with bulky substituents to produce amorphous polycarbonates with high heat resistance APEC (Bayer) and Lexan (Sabic), however, the glass transition temperature (Tg) of these polymers is much higher than 200 ° C (238 ° C and 250 ° C, respectively) ) It is possible to lower the glass transition temperature of polymers using bisphenols that form homopolymers with initially low Tg, for example, based on bisphenol A (147 ° C). Thus, copolycarbonates based on bisphenol A and bisphenols with bulky substituents will have an intermediate glass transition temperature between 147 ° C and 238 ° C.

It is also known about the possibility of synthesizing polycarbonates containing fluorophore fragments that give luminescent properties to polymers (Smirnova OV, Erofeeva SB Polycarbonates. - M .: Chemistry, 1975).

Thus, the invention proposes to use a colorful composition containing as a binder in an amount of from 0.1 to 10.0% by weight of a polycarbonate derivative (copolymer) having luminescent properties based on geminally substituted dihydroxyphenylalkane, bisphenol A and fluorophore of the following formula:

where R ₁ is hydrogen or alkyl (C ₁ -C ₃ );

R ₂ is alkyl (C ₅ -C ₈ ), cycloalkyl (C ₅ -C ₆ ), arylalkyl (C ₇ -C ₁₂ );

R ₃ is a fluorophore;

n, m, k are integers indicating the number of functional structural units in the molecule of the polycarbonate derivative, and the ratio n / (n + m + k) is from 0.60 to 0.80; the ratio m / (n + m + k) is from 0.15 to 0.30; the ratio k / (n + m + k) is from 0.05 to 0.10.

The number of functional structural units in the molecule of the polycarbonate derivative (ratio n, m, k) determines the parameters of the suitability of the polymer for use as a binder in inkjet inks: solubility, glass transition temperature, molecular weight and luminescent properties.

The polycarbonate derivative has an average molecular weight (average weight value) of at least 10,000, preferably from 20,000 to 100,000, and also has a glass transition temperature of from 150 to 190 ° C, preferably from 170 to 180 ° C.

As geminally disubstituted dihydroxyphenylalkane, in principle, any bisphenols corresponding to the above formula can be used, provided that they should increase the solubility of the polymer in non-halogenated solvents.

Such bisphenols preferably include compounds containing bulky alkyl, cycloalkyl and arylalkyl substituents at the central carbon atom. For example, bis- (4-hydroxyphenyl) cyclohexylmethane; 1,1-bis- (4-hydroxyphenyl) -1-cyclohexylbutane; 1,1-bis- (4-hydroxyphenyl) -1-phenylbutane and others.

As the fluorophores in the invention, in principle, any known organic compounds having luminescent properties can be used, which can be included in the composition of the polycarbonate derivative as structural units, while not impairing or slightly deteriorating the physicochemical properties of the final polymer and imparting it luminescent properties. A fluorophore is a structural fragment of a molecule that gives it luminescent properties. A fluorophore or its structural fragments may also have chromophore properties, that is, colorize chemical compounds, thereby determining their color.

Depending on the chemical structure, fluorophores can be assigned to the following classes (Krasovitsky BM, Bolotin BM Organic phosphors. - M .: Chemistry, 1984): aromatic hydrocarbons and their derivatives (polyphenyl containing condensed aromatic nuclei or arylethylene and aryl acetylene groups); compounds containing heteroatoms (five-membered and six-membered heterocycles); metal complexes with organic ligands; compounds with a carbonyl group.

Preferred fluorophores include compounds based on benzoxazole, phenanthroxazole, aromatic α-diketones, as well as rare earth complexes.

The solvent for the colorful composition can be either water-based (i.e., contain up to 20% by weight of water, the rest is organic solvents), and based on organic solvents (up to 5% by weight of water). The solvent should preferably be halogen free. The solvent may preferably be or consist of aliphatic, cycloaliphatic, aromatic hydrocarbons; simple or complex organic esters; derivatives of γ-butyrolactam or γ-butyrolactone.

As the solvent, individual solvents or solvent mixtures can be used, such as aliphatic, cycloaliphatic, aromatic hydrocarbons, for example mesitene, 1,2,4-trimethylbenzene, cumene and solvent naphtha, toluene, xylene, (organic) esters, for example methyl acetate , ethyl acetate, butyl acetate, methoxypropyl acetate, ethyl 3-ethoxypropionate, diethylene and dimethyl ethers of diethylene glycol, as well as N-methylpyrrolidone and γ-butyrolactone.

Suitable solvent mixtures include, for example: a) from 0 to 10 mass. %, preferably from 1 to 5 mass. %, primarily from 2 to 3 mass. % mesitylen, b) from 10 to 50 mass. %, preferably from 25 to 50 mass. %, primarily from 30 to 40 mass. % 1-methoxy-2-propanol acetate, c) from 0 to 20 wt. %, preferably from 1 to 20 mass. %, primarily from 0 to 15 mass. % 1,2,4-trimethylbenzene, g) from 10 to 50 mass. %, preferably from 25 to 50 mass. %, primarily from 30 to 40 mass. % ethyl 3-ethoxypropionate, d) from 0 to 10 mass. %, preferably from 0.01 to 2 mass. %, primarily from 0.05 to 0.5 mass. % cumene and from 0 to 80 mass. %, preferably from 1 to 40 mass. %, primarily from 15 to 25 mass. % solvent-naphtha, while the sum of the components from a) to e) is constantly 100 mass. %

As a colorant in the invention, in principle, any colorant or a mixture of colorants that impart coloring properties to the ink composition (ink) can be used. Dye refers to organic and inorganic coloring materials, both solvent-soluble compositions and pigments insoluble in the solvent, with a particle size of not more than 1.0 μm. These dyes and pigments are described in detail in the literature (Ullmann’s Encyclopedia of Industrial Chemistry electronic publishing, Willey, 2007).

Colorants can be cationic, anionic, and also neutral. Only as examples used in the inkjet printing of dyes can be mentioned: diamond black (C.I. 28440), chromogenic black (C.I. 14645), direct intense black E (C.I. 30235), natural black salt B (C.I. 37245), natural black salt K (C.I. 37190), Sudan black HB (C.I. 26150), naphthol black (C.I. 20470), Bayscript® black liquid, C.I. basic black 11, C.I. primary blue 154, Cartasol® turquoise K-ZL fluid, Cartasol® turquoise K-RL liquid (C.I. primary blue 140), Cartasol® blue K5R liquid. In addition, commercially available Hostafine® dyes black TS liquid (sold by Clariant GmbH, Germany), Bayscript® black liquid (C.I. mix, sold by Bayer AG, Germany), Cartasol® black MG liquid ( C.I. primary black 11, registered trademark of Clariant GmbH, Germany), Flexonylschwarz® PR 100 (E C.I. 30235, sold by Hoechst AG), Rhodamine B, Cartasol® orange K3 GL, Cartasol® yellow K4 GL , Cartasol® K GL, or Cartasol® red K-3B. In addition, anthraquinone, azo, quinophthalone, coumarin, methine, perinone, and / or pyrazolating agents, for example commercially available under the trademarks Macrolex®, can be used as soluble dyes.

The functional material of the colorful composition includes a functional material or a mixture of functional materials that serve as anti-counterfeiting elements. These materials in the printed image can be visualized by the human eye only with the use of auxiliary technical means or detected by a special device. As such materials, Stokes or anti-Stokes phosphors, photochromes, thermochroms, as well as substances intensively absorbing in the near infrared range of the electromagnetic spectrum can be used. The chemicals used as a functional material can have both organic and inorganic nature, but they must either have solubility in the solvent of the composition or have a particle size of not more than 1.0 microns to prevent clogging of the print head nozzles during inkjet printing . In addition, they must be stable (do not decompose and do not change their physicochemical properties) at temperatures up to 200 ° C.

Examples of functional materials of the colorful composition include such substances as benzoxazole-based organic Stokes phosphors with long alkyl substituents (to improve solubility in non-halogenated solvents), NaYF ₄ based anti-Stokes inorganic phosphors based on NaYF ₄ : Er, Yb, dithiolene based IR absorbers transition metal complexes also with long alkyl substituents.

Excipients of the ink composition contain excipients traditionally used in inkjet inks, such as wetting agents, dispersants, defoamers, stabilizers (light), preservatives, biocides, viscosity regulators, buffer systems, etc., which regulate printing and technical and operational properties ink. As thickeners, for example, other polymers and thickening salts (sodium lactate) soluble in the colorful composition can be used. As biocides, for example, Proxel®GXL and Parmetol®A26 can be used. As dispersants, for example, industrial inkjet dispersants such as BykJet 9151 and BykJet 9152 can be used. As buffer systems (for water-based ink compositions), they stabilize the pH in the range from 2.5 to 8.5 especially from 5 to 8, systems based on lithium acetate, buffer borate, triethanolamine or acetic acid / sodium acetate can be used. As viscosity regulators, for example, block copolymers of the Pluronic® product line can be used.

Excipients also include other components, such as, for example, acetic acid, formic acid, or N-methylpyrrolidone (which not only acts as a solvent for the colorful composition, but also has the ability to dissolve the top layer of polycarbonate films to better fix the paint composition in question) as well as polymers that are part of the solutions of coloring substances or coloring pastes.

Examples

Example 1. Synthesis of polycarbonate derivative No. 1

136.98 g (0.6 mol) of bisphenol A (2,2-bis- (4-hydroxyphenyl) propane), 84.71 g (0.3 mol) of bis- (4-hydroxyphenyl) cyclohexylmethane, 24, 22 (0.1 mol) of 4,4'-dihydroxybenzene, 336.6 g (6 mol) of KOH are dissolved in 2700 g of water in an inert atmosphere with stirring. Then a solution of 1.88 g of phenol in 2500 ml of methylene chloride is added. With vigorous stirring, 108.8 g (0.367 mol) of triphosgene are introduced into the solution at a pH of 13 to 14 and at a temperature of 21 to 25 ° C. Then add 1 ml of ethyl piperidine and mix for another 45 minutes. The aqueous phase that does not contain sodium bisphenolate is separated, and the organic phase after oxidation with phosphoric acid is washed with water until neutral and the solvent is removed in vacuo.

A polycarbonate copolymer having the following structural formula:

showed a relative solution viscosity of 1.355. The ratio n / (n + m + k) was 0.6, the ratio m / (n + m + k) was 0.3, the ratio k / (n + m + k) was 0.1, which corresponds to the ratio n / m / k equal to 0.6 / 0.3 / 0.1. The glass transition temperature of this polymer was 163 ° C (DSC). The molecular weight of the obtained polymer was 21300.

Example 2. Synthesis of polycarbonate derivative No. 2

159.81 g (0.7 mol) of bisphenol A (2,2-bis- (4-hydroxyphenyl) propane), 64.89 g (0.2 mol) of 1,1-bis- (4-hydroxyphenyl) - 1-cyclohexylbutane, 27.23 (0.1 mol) ethyl (bis- (4-hydroxyphenyl) acetate), 336.6 g (6 mol) KOH are dissolved in 2700 g of water in an inert atmosphere with stirring. Then a solution of 1.88 g of phenol in 2500 ml of methylene chloride is added. With vigorous stirring, 108.8 g (0.367 mol) of triphosgene are introduced into the solution at a pH of 13 to 14 and at a temperature of 21 to 25 ° C. Then add 1 ml of ethyl piperidine and mix for another 30 minutes. The aqueous phase that does not contain sodium bisphenolate is separated, and the organic phase after oxidation with phosphoric acid is washed with water until neutral and the solvent is removed in vacuo. The resulting polymer intermediate is dissolved in 3500 ml of ethyl alcohol and, with vigorous stirring, a solution of 33.8 g (0.1 mol) of europium nitrate and 43.2 (0.2 mol) of benzoyltrifluoroacetone in 500 ml of ethyl alcohol are added to it. The reaction mass is stirred for 20 minutes and then approximately 400 ml of concentrated aqueous ammonia solution is added dropwise until the precipitate completely precipitates. The precipitate formed is filtered off and washed on the filter with isoropyl alcohol 5 times in 200 ml portions. The washed polymer is dried in air.

A polycarbonate copolymer having the following structural formula:

demonstrated a relative solution viscosity of 1.389. The ratio n / (n + m + k) was 0.7, the ratio m / (n + m + k) was 0.2, the ratio k / (n + m + k) was 0.1, which corresponds to the ratio n / m / k equal to 0.7 / 0.2 / 0.1. The glass transition temperature of this polymer was 189 ° C (DSC). The molecular weight of the obtained polymer was 11700.

Example 3. Synthesis of polycarbonate derivative No. 3

182.64 g (0.8 mol) of bisphenol A (2,2-bis- (4-hydroxyphenyl) propane), 47.76 g (0.15 mol) of 1,1-bis- (4-hydroxyphenyl) - 1-phenylbutane, 12.11 (0.05 mol) of 4,4'-dihydroxybenzene, 336.6 g (6 mol) of KOH are dissolved in 2700 g of water in an inert atmosphere with stirring. Then a solution of 1.88 g of phenol in 2500 ml of methylene chloride is added. With vigorous stirring, 108.8 g (0.367 mol) of triphosgene are introduced into the solution at a pH of 13 to 14 and at a temperature of 21 to 25 ° C. Then add 1 ml of ethyl piperidine and mix for another 45 minutes. The aqueous phase that does not contain sodium bisphenolate is separated, and the organic phase after oxidation with phosphoric acid is washed with water until neutral and the solvent is removed in vacuo.

A polycarbonate copolymer having the following structural formula:

showed a relative solution viscosity of 1.298. The ratio n / (n + m + k) was 0.8, the ratio m / (n + m + k) was 0.15, the ratio k / (n + m + k) was 0.05, which corresponds to the ratio n / m / k equal to 0.8 / 0.15 / 0.05. The glass transition temperature of this polymer was 174 ° C (DSC). The molecular weight of the polymer was 17500.

Example 4. Synthesis of polycarbonate derivative No. 4

159.81 g (0.7 mol) of bisphenol A (2,2-bis- (4-hydroxyphenyl) propane), 78.11 g (0.25 mol) of 4,4-bis- (4-hydroxyphenyl) - nonane, 17.37 (0.05 mol) 2- (2'-OH-phenyl) - (2,7-dihydroxy-9,10-phenantro) -oxazole, 336.6 g (6 mol) KOH is dissolved in 2700 g of water in an atmosphere of inert gases with stirring. Then a solution of 1.88 g of phenol in 2500 ml of methylene chloride is added. With vigorous stirring, 108.8 g (0.367 mol) of triphosgene are introduced into the solution at a pH of 13 to 14 and at a temperature of 21 to 25 ° C. Then add 1 ml of ethyl piperidine and mix for another 45 minutes. The aqueous phase that does not contain sodium bisphenolate is separated, and the organic phase after oxidation with phosphoric acid is washed with water until neutral and the solvent is removed in vacuo.

A polycarbonate copolymer having the following structural formula:

showed a relative solution viscosity of 1.305. The ratio n / (n + m + k) was 0.7, the ratio m / (n + m + k) was 0.25, the ratio k / (n + m + k) was 0.05, which corresponds to the ratio n / m / k equal to 0.7 / 0.25 / 0.05. The glass transition temperature of this polymer was 191 ° C (DSC). The molecular weight of the polymer was 22300.

Example 5. Synthesis of polycarbonate derivative No. 5

159.81 g (0.7 mol) of bisphenol A (2,2-bis- (4-hydroxyphenyl) propane), 59.68 g (0.2 mol) of 1,1-bis- (4-hydroxyphenyl) - 1-isopropylbutanan, 22.72 (0.1 mol) 2- (4-hydroxyphenyl) -1,3-benzoxazole-6-ol, 336.6 g (6 mol) KOH is dissolved in 2700 g of water in an inert atmosphere under stirring. Then a solution of 1.88 g of phenol in 2500 ml of methylene chloride is added. With vigorous stirring, 108.8 g (0.367 mol) of triphosgene are introduced into the solution at a pH of 13 to 14 and at a temperature of 21 to 25 ° C. Then add 1 ml of ethyl piperidine and mix for another 120 minutes. The aqueous phase that does not contain sodium bisphenolate is separated, and the organic phase after oxidation with phosphoric acid is washed with water until neutral and the solvent is removed in vacuo.

A polycarbonate copolymer having the following structural formula:

demonstrated a relative solution viscosity of 2.735. The ratio n / (n + m + k) was 0.7, the ratio m / (n + m + k) was 0.2, the ratio k / (n + m + k) was 0.1, which corresponds to the ratio n / m / k equal to 0.7 / 0.2 / 0.1. The glass transition temperature of this polymer was 187 ° C (DSC). The molecular weight of the polymer was 64100.

All synthesized polycarbonate derivatives had solubility in non-halogenated solvents and had luminescence under the influence of UV radiation (λ _max = 365 nm). The polycarbonate derivative of example 2 also had the property to significantly increase the luminescence intensity under the influence of UV radiation when cooled from room temperature to a temperature below minus 45 ° C.

Example 6. The manufacture of solvent inkjet ink No. 1

10 g (10 wt.% In terms of the total weight of the ink composition, hereinafter referred to as wt.%) Of the polycarbonate derivative of Example 1 was dissolved using a magnetic stirrer in 5 g (5 wt.%) Of N-methylpyrrolidone and 90 g ( 90 wt.%) Solvent mixtures of the following composition:

- diethylene glycol diethyl ether (75%);

- butyl glycol acetate (18%);

- 1,2,4-trimethylbenzene (2%);

- tetraethylene glycol dimethyl ether (5%).

Thus, a colorless solution with a viscosity at room temperature of 3.77 mPa · s was obtained. The surface tension of this solution was determined using a measuring system by the hanging drop method and amounted to 27.4 mN / m. This solution can be used for inkjet printing of colorless images under daylight that will luminesce when irradiated with UV radiation.

Example 7. The manufacture of solvent inkjet ink No. 2

Analogously to example 6, transparent ink was made using 0.1 g (0.1 wt.%) Of the polycarbonate derivative from example 2, 0.1 g (0.1 wt.%) Of the organic phosphor Orlum 490RT (LLC Olbo) and 99.8 g (99.8 wt%) of the solvent mixture of Example 6. The resulting colorless, low-viscosity solution had a surface tension of 23.7 mN / m and a viscosity at room temperature of 1.75 mPa · s. This solution can be used for inkjet printing of colorless images under daylight that will luminesce when irradiated with UV radiation.

Example 8. The manufacture of solvent inkjet ink No. 3

5 g (5 wt.%) Of the polycarbonate derivative of example 3 was dissolved using a magnetic stirrer in 70 g (70 wt.%) Of the solvent mixture of example 6.

Then, 25 g of pigment paste made in a bead mill using 5 g (5 wt.%) Of Ink Jet Magenta E5B pigment (“Clariant”) and 5 g (5 wt.%) Of BykJet 9151 dispersant and 5 g (5 wt.%) Of N-methylpyrrolidone and 10 g (10 wt.%) Of the solvent mixture of Example 6.

Thus, luminescent magenta inks with a solution viscosity at room temperature of 4.35 mPa · s were obtained. The surface tension of these inks was determined using a measuring system using the hanging drop method and amounted to 29.7 mN / m.

Example 9. The manufacture of solvent inkjet ink No. 4

Analogously to example 8, black ink was made using 5 g (5 wt.%) Of a polycarbonate derivative from example 1, 1 g (1 wt.%) Of pigment Special Black 250 ("Clariant") and 0.5 g (0.5 wt. wt.%) BykJet 9152 dispersant and 5 g (5 wt.%) of the organic phosphor Orlum 600РТ (Olbo LLC) and 5 g (5 wt.%) of N-methylpyrrolidone and 83.5 g (83.5 wt.%) solvent mixtures from example 6.

Black fluorescent inks had a solution viscosity at room temperature of 3.01 mPa · s and a surface tension of 28.2 mN / m.

Example 10. The manufacture of solvent inkjet ink No. 5

2 g (2 wt.%) Of the polycarbonate derivative of Example 5, 0.1 g (0.1 wt.%) Of a nanoscale anti-Stokes inorganic phosphor based on NaYF ₄ : Er, Yb, 0.1 g (0.1 wt.%) ) IR absorber based on a transition metal dithiene complex, 1 g (1 wt.%) Of Solvent Blue 104 dye (C.I. No. 61568), 0.2 g (0.2 wt.%) UV absorber (light stabilizer) Tinuvin 320, 1 g (1 wt.%) Polymer (viscosity regulator) Vinnol Н 15/42 TF and 0.1 g (0.1 wt.%) Antifoam Penta 461 was dissolved using a magnetic stirrer in 90.5 g ( 90.5 wt.%) Solvent mixtures from example 6 and 5 g (5 wt.%) Of N-methylpyrrolidone.

Thus, blue inks luminescent under the influence of UV and IR radiation were obtained with a solution viscosity at room temperature of 6.27 mPa · s. These inks also possessed the ability to absorb radiation in the near infrared range. The surface tension of these inks was determined using a measuring system using the hanging drop method and amounted to 31.2 mN / m.

Example 11. Solvent Ink Printing

On inkjet printer "VersaStudio BN-20" ("Roland"), printing was performed with manufactured inks No. 1, No. 2, No. 3, No. 4 and No. 5, as well as branded inks of the ECO-SOL MAX brand ("Roland") with a variation various printing parameters for polycarbonate films of the VERIFOIL brand, with a thickness of 50, 100, 200 and 300 microns.

Thus, the following images were printed on the indicated polycarbonate films: photographic (bitmap), text and spot (vector), while the paint layer occupied from 1% to 99% (1%, 10%, 50%, 75%, 99 %) frontal area of subsequently manufactured plastic cards (multilayer polycarbonate composite).

All printed samples of polycarbonate films showed satisfactory print quality with all ink samples.

Example 12. The manufacture of multilayer polycarbonate composites (plastic cards)

All inkjet polycarbonate films of Example 11 were laminated to produce ID-1 polycarbonate plastic cards using the OLA6H LAMINATOR (OASYS) laboratory sheet laminator. The lamination time was 50 minutes. The maximum temperature during the lamination process was 180 ° C. Maximum pressure 13 bar.

Example 13. The manufacture of multilayer polycarbonate composites (plastic cards)

All inkjet polycarbonate films of Example 11 were laminated to produce ID-1 polycarbonate plastic cards using the Melzer industrial lamination line. The lamination time was 30 s. The maximum temperature during the lamination process was 175 ° C. Maximum pressure 100 bar.

Example 14. The manufacture of multilayer polycarbonate composites (plastic cards)

Analogously to example 13, where the maximum temperature during the lamination process was 190 ° C.

For all manufactured plastic card options, the following was observed:

- in the print area of the image with ECO-SOL MAX inkjet ink containing a binder based only on a copolymer of vinyl chloride and vinyl acetate, the upper lamination polycarbonate film was peeled off;

- in the print zone of the image with inkjet ink No. 1, No. 2, No. 3, No. 4 and No. 5, containing a binder based on a polycarbonate derivative (derivative), consisting of functional structural units of geminically disubstituted dihydroxyphenylalkane, bisphenol A and fluorophore, peeling of the upper lamination polycarbonate the film did not occur.

These results indicate that a monolithic polycarbonate composite resistant to delamination is obtained, which contains protected color images. This is ensured by the use of a polycarbonate derivative based on gemini disubstituted dihydroxyphenylalkane as a binder for inkjet ink.

Claims (37)

1. Colorful composition containing, mass. %: a binder comprising a polycarbonate derivative based on geminally substituted dihydroxyphenylalkane - 0.1-10.0; dye or a mixture of dyes - 0.0-5.0; functional material or a mixture of functional materials - 0,0-5,0; excipients - 0.0-10.0; solvent or mixture of solvents - up to 100%, while the polycarbonate derivative has luminescent properties and contains functional structural units of carbonates, connected statistically or block according to the formula

Where R ₁ is hydrogen or alkyl (C ₁ -C ₃ ); R ₂ is alkyl (C ₅ -C ₈ ), cycloalkyl (C ₅ -C ₆ ), arylalkyl (C ₇ -C ₁₂ ); R ₃ is a fluorophore; n, m, k are integers indicating the number of functional structural units in the molecule of the polycarbonate derivative, and the ratio n / (n + m + k) is from 0.60 to 0.80; the ratio m / (n + m + k) is from 0.15 to 0.30; the ratio k / (n + m + k) is from 0.05 to 0.10. 2. The colorful composition according to claim 1, characterized in that the polycarbonate derivative has an average molecular weight (average weight value) of at least 12,000, preferably from 20,000 to 64,000. 3. The colorful composition according to claim 1, characterized in that the polycarbonate derivative has a glass transition temperature from 163 to 190 ° C, preferably from 170 to 180 ° C. 4. The colorful composition according to claim 1, characterized in that the polycarbonate derivative is colorless or slightly colored. 5. The colorful composition according to claim 1, characterized in that the polycarbonate derivative has a saturated color. 6. The colorful composition according to claim 1, characterized in that the polycarbonate derivative luminesces under the influence of UV radiation at room temperature. 7. The colorful composition according to claim 6, characterized in that the polycarbonate derivative significantly increases the luminescence intensity under the influence of UV radiation when cooled from room temperature to a temperature below minus 45 ° C. 8. The colorful composition of claim 1, wherein R ₁ is preferably alkyl (C ₁ -C ₃ ), R ₂ is preferably cycloalkyl (C ₅ -C ₆ ). 9. The colorful composition according to claim 1, characterized in that the fluorophore R ₃ is preferably a phenantrooxazole derivative. 10. The colorful composition according to claim 1, characterized in that the fluorophore R ₃ is preferably a benzoxazole derivative. 11. The colorful composition according to claim 1, characterized in that the fluorophore R ₃ is preferably a rare earth metal carboxylate bis diketonate derivative. 12. The colorful composition according to claim 1, characterized in that the fluorophore R ₃ is preferably a derivative of aromatic α-diketone. 13. The colorful composition according to claim 1, characterized in that the solvent does not contain halogens. 14. The colorful composition according to claim 1, characterized in that the solvent component consists of an aliphatic and / or cycloaliphatic and / or aromatic hydrocarbon, a simple and / or complex organic ester, a derivative of γ-butyrolactam and / or γ-butyrolactone and / or mixtures of such solvents. 15. The colorful composition according to claim 1, characterized in that the dye is a solvent-insoluble coloring pigment. 16. The colorful composition according to claim 1, characterized in that the functional material is a Stokes or anti-Stokes phosphor. 17. The colorful composition according to claim 1, characterized in that the functional material is a dye that absorbs in the near infrared range of the electromagnetic spectrum. 18. A multilayer polycarbonate composite, such as a plastic card, an identification document or a valuable document, characterized in that it contains at least one ink layer, occupying from 1% to 99% of the frontal projection area of the composite and made with the colorful composition according to any one of paragraphs. 1-17. 19. A multilayer polycarbonate composite according to claim 18, characterized in that the ink layer is a photographic image or part thereof. 20. A multilayer polycarbonate composite according to claim 18, characterized in that the ink layer is a text image or part thereof. 21. A multilayer polycarbonate composite according to claim 18, characterized in that the ink layer is a raster or vector pattern or part thereof. 22. A method of manufacturing a multilayer polycarbonate composite according to any one of paragraphs. 18-21, characterized in that at a certain stage before the layers are combined into a single monolithic composite, at least one of the layers is coated with a colorful composition according to any one of paragraphs. 1-17. 23. A method of manufacturing a multilayer polycarbonate composite according to claim 22, characterized in that the colorful composition is applied by inkjet printing. 24. A method of manufacturing a multilayer polycarbonate composite according to p. 22, characterized in that the colorful composition is applied to the polymer film with a thickness of 50 microns to 300 microns. 25. A method of manufacturing a multilayer polycarbonate composite according to p. 22, characterized in that the connection of the layers into a single monolithic composite is carried out by lamination under pressure from 13 to 100 bar and a temperature of 175 ° C to 190 ° C for a given period of time.