Printing ink system for printing on polyamide-based casings for food products, printed casings for food products and method for production thereof

FIELD: chemistry.

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

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

27 cl, 1 ex

 

The invention relates to a system of printing inks for printing on films based on polyamide, napechatanny them single or multilayer films, used as wrappers for food products such as artificial sausage casings, and the way they are received.

Containing print wrappers for food products are widely used in the food industry, for example, as packaging for sausages, cheese or cooked dishes. A significant part of the used membranes for food is based single or multi - layer shell-bearers of thermoplastic polymers, the surface of which has a multi-color printing. For packaging of many varieties of sausage are required shrinkable casings for food products.

Sausage casings printing can be obtained in various conventional ways of printing. In practice implemented in two ways: flexographic printing and gravure printing printing. Sausage casings are usually nadrachivat on the outer side, as regulations health surveillance in many countries it is prohibited direct contact printing ink with sausage stuffing. Only for sausage casings of a multilayer synthetic fabrics, which after the formation of the sleeve receive the suture, there is a possibility to place a seal between two protecting layers For this is often used deep cleaning the print. Print on sausage casings should be performed so that the print did not change either during storage and processing of sausage casings or the sale of ready-made sausages, and in order to avoid any negative side effects. Accordingly, a printed layer must meet the following requirements:

neutral behaviour towards the shell-media

- neutral behaviour towards the filler (sausage stuffing),

- resistance to grease and water,

- resistance to salt and marinade

- resistance to spices and seasonings,

- temperature resistance,

- inertness to smoke smoke,

- abrasion resistance,

- resistance to ageing,

resistance,

- resistance to change size, i.e. the passion of the imprint of the sausage casing in the processes of stretching and sitting room.

Paint used for flexographic printing, are usually paints in a solution of a solvent having a relatively low solids content, which should be the lower, the higher the printing speed. They consist of pigments, binders, additives and solvent or mixture of solvents. For color printing, the membrane-substrate, on which the printing passes through several points in color, which is applied on one printing ink For certain sausage casings, for example monochrome synthetic membranes, light, in particular white, shades of paint are printed twice to obtain a sufficient saturation of the print.

Modern printing machines which are used for printing on plastic films, in particular sausage casing on the basis of synthetic material, are the so-called machines with a Central location of the cylinder, which are equipped with colour enhancing mechanisms, up to 8. Points colouring they are set around a large, often water-cooled cylinder. The shell carrier is conducted around the Central cylinder and points of color in conditions identical tension cover the paint with a different color.

Printing machines have the following principle: the shell-carrier facing in paragraph unwinding from the roll, is the guide rollers and is mounted on the rolls of the so-called device control edges. After that, in order to prepare for print media is carried out through the corona treatment, which in the case of shells-carriers from natural raw materials (cellulose, collagen, tissue, etc. should not be used. Coming from the shell-carrier rollers fit around the Central cylinder and is held by the items color and cover the W printing. Between the printing mechanisms are drying device, which is dried printing ink before each print. Then covered with a seal, the shell carrier passes through a tunnel dryer, in which the final drying, mainly heated air and/or emitters. After conditioning and optional dusting powder as a strip finished lower shell with printing again wound.

Points colouring consist of a dye bath, which is filled with printing ink, one or more rollers, metering of the paint and roll clichés, which strengthened laser engraved rubber clichés or cliches of the photopolymer resin. For large print runs clichés can be laser engraved directly on the synthetic surface of the cylinder. Such printing cylinders are called cylinder for tubular forms. Rollers, metering paint, can be rubber or plastic rollers or rollers with mesh surface of the metal and ceramic surfaces and with or without printing device. When the high-speed printing dyeing bath can be closed at the doctor device. In this case we speak of a chamber doctor blade devices. Using a roller-dosing convex part of the surface of the cliché on the roll-cliche moistened print the oops paint, which is transferred therefrom to the surface of the shell carrier. At the end of the paint used, the solvent should be removed by drying in air or by heating in a tunnel dryer. At the end of the shell-media wound and may become necessary after the curing time is Packed.

As printing inks are applied:

- component inks for flexographic printing, solvent-based or solvent mixture,

- component inks for flexographic printing, curing irradiation,

- two-component inks for flexographic printing, so-called reactive dyes, which consist of coloring and hardening components.

One-component ink for flexographic printing, solvent-based can be printed without preparation, if you ignore the correct viscosity of printing ink. These paints have a limited scope, as they are due to their low adhesion are not suitable for all polymeric membranes vehicles.

Cured under irradiation one-component ink for flexographic printing is used for printing on polymeric membrane-substrate only recently, and is achieved as close to as deep cleaning the print. Curing at the yeseniya printing on polymer shell carrier is carried out by means of UV radiation, which creates a mercury quartz emitters. This method of printing is also known as flexographic printing with UV-curable inks. In principle, there are two differently arranged in the form of a UV-curable printing inks: ink, cured in the radical chemical reactions, and other cationic curing. Shell food preferably used cation-curable inks, as they in their composition correspond to the regulations food law and, in addition, have the best consumer properties. UV-curable printing ink prepared without solvents, and therefore not subject to the laws and regulations on combustible liquids. Sausage casings with the seal does not contain residues of the solvent. The paint can be printed without problems and with a high speed, and it allows small bitmap printing density to 65 lines per cm, which is equivalent to gravure printing. UV-curable printing ink suitable for screen printing in four colors". In the layers or combinations of printing dots are perceived by the human eye as different colors. So, for example, by a layer-by-layer printing yellow and blue dot, you can get a green mark. During curing printing inks UV radiation contained in printing inks is photoinitiator starts the polymerization, which leads to the curing of printing inks. In the respective printing machines quartz emitters, creating UV radiation, is placed between points colouring, so that you no longer need any tunnel drying.

In the case of two-component inks for flexographic printing, which are applied with the addition of hardener components should be mixed in a certain ratio immediately before printing and can be used within the prescribed time, that was chemically induced cross-linking of printing ink on the surface of the shell carrier. Due to the limited processing time, small "viability" and the inability to re-use these coloring compositions cause the high cost of printing.

There are several variants of two-component inks for flexographic printing, which differ in the use of different solvents, namely, printing inks, solvent-based, alcohols and water. Because of the long reaction time, which usually ranges from 2 to 3 days, delayed filling. On the other hand, the addition of the curing agent promotes adhesion of paint to the surface of the sausage casing, so, thereby, you can also safely and with good adhesion to print sheath derived from natural raw materials, such as, for example, call the eh, the pulp tissue.

In document WO 02/081576 described aqueous UV-curable composition for printing and coating, which contains:

- water as solvent,

- water-soluble component with at least one α,β-ethylene unsaturated radiation-curable group,

the dyes or pigments on the selection and

- photoinitiator and choice, which upon irradiation with ultraviolet light to form free radicals.

Preferably, the water-soluble component is a water-soluble oligomer having two or more acrylate groups. In addition, the document WO 02/081576 refers to the way in which the media covered or napechatala composition, and then this composition is cured by UV-irradiation with the receiving film. As the printing method is mentioned, among others, flexographic printing. As the media describes packaging materials for food products from various thermoplastic polymers such as polyamide. The cured film has good adhesion to the media, as well as high abrasion resistance. However, water compositions require more time for drying and therefore poorly suited for the desired high-speed printing.

In EP 0 741 644 B1 describes a method of flexographic printing on food packaging, in which the heat-shrinkable flexible Polo who have put several layers of cured UV ink and partially accordingly fully utverjdayut by irradiation with ultraviolet radiation (UV) or electron (electron beam, EB). When freshly applied ink partially otverzhdajutsja UV radiation between points dyeing machines for flexographic printing, and then the entire seal hardens when exposed to EB. The number of photoinitiators in radiation curable printing ink can be less than 10 wt.%. Applying primer before printing is not mentioned. Also not mentioned are no packages on the basis of polyamide or copolyamid, which could not well be applied by printing with UV-curable inks.

In DE 601 22 503 described ink system in combination with a covering lacquer system for flexographic printing on heat shrink polymer packing casings for food products. By printing packaging shell can consist of polyamides, such as nylon. Cured by electron beams or ultraviolet radiation (UV) coating of lacquer system contains:

i) monomers with low viscosity (reactive diluents),

(ii) oligomers/prepolymers (e.g., acrylates) and, if necessary,

iii) other additives, as chemically inactive plasticizer-solvent.

Curing lacquer coating systems, preferably based on the radical is the second mechanism. UV lacquer coating systems contain one or more photoinitiators. Ink system may be radiation curable and can contain one or more pigments (e.g., pigments) together with the monomers and oligomers/prepolymers (similar coating of lacquer systems).

Radiation curable ink system preferably contains almost no photoinitiator. Before applying ink system packaging casing can be primed. However, the application and curing of coating lacquer means an additional working step, which makes the method generally unprofitable.

In the industry of food packaging, there is a need in printing systems that do not contain solvents and mostly curable with ultraviolet light, which do not require subsequent curing of electronic rays. They should be suitable in particular for flexographic printing, and allow high speed printing (up to 150 m/min or more). In particular, it must be possible to print them on surfaces, which consist mainly of polyamides and/or copolyamids. While the imprint must cling on the media, and not subject to change under the influence of oils or fats, hot water or other substances encountered in obtaining packaged products : what I.

Object of the invention is to produce a print of a film based on (co)polyamide, in particular napechatannoe tubular casings for food products based on (co)polyamide, which has the following properties:

- strong adhesion to the surface of the shell, even without any prior surface treatment by corona discharge;

- high resistance to wear and scratching;

- resistance to mechanical and thermal stress, which is exposed to the food product, such as sausage, filling, packaging, further processing, storage and transportation;

weak residual odor;

- no negative impact on the taste of the food that comes into contact with the seal;

- less than 10 mg/DM2extractable residues,

- does not require varnishing;

- non-use of aqueous printing inks;

- you can get very shiny print or print from matte to very matte.

This problem is solved using a system of printing inks, which consists of dirt paint and at least one radically-curable printing inks. Dirt paint as the main component contains a compound having two different types of reactive groups. One of them can form a bond with the surface of the (co)polyamide, in particular, potenially (poly)condensation. Groups of another type are the groups with ethylene unsaturation, which may be in initiated radical polyaddition reaction. This involves, in particular, (meth)acrylate groups.

Thus, the object of the invention is the system of printing inks for printing on the film surface based on (co)polyamide-side printing, with a radically-curable with primer and at least one printing ink, radically curable under the action of UV radiation, and soil ink contains a reactive compound which is in the same molecule contains:

a) at least one group that can form a bond with the surface of the (co)polyamide, and

b) at least one group with ethylene unsaturation, which can join-initiated radical polyaddition reaction.

Reactive compound is a monomer, oligomer and/or prepolymer. Particularly suitable low viscosity monomers with a radical-polymerizable olefinic double bonds, preferably di(meth)acrylate of tripropyleneglycol, di(meth)acrylate of dipropyleneglycol, di(meth)acrylate of hexandiol or three(meth)acrylate of trimethylolpropane. The group that can form a bond with the surface of the (co)polyamide is an isocyanate group. As groups with ethylene unsaturation is used (meth)acrylate group.

Radical-curable dirt paint may contain monomers, oligomers and/or prepolymers with polymerizable ethylene-unsaturated groups, curing radicals when exposed to UV radiation or electron beams.

As monomers preferably used in the following connections: three(meth)acrylate of trimethylolpropane, di(meth)acrylate of hexanediol, di(meth)acrylate 1,3-butyleneglycol, di(meth)acrylate diethylene glycol, 1,6-hexanediamine, di(meth)acrylate neopentyl glycol, di(meth)acrylate of polyethylene glycol-200, diacrylate tetraethyleneglycol, diacrylate triethylene glycol, Tetra(meth)acrylate of pentaerythritol, diacrylate tripropyleneglycol, ethoxylated di(meth)acrylate of bisphenol a, mono - or propylene glycol dimethacrylate, three(meth)acrylate of trimethylolpropane, tetraacrylate of trimethylolpropane, triacrylate Tris(hydroxyethyl)isocyanurate, hydroxypentanal of dipentaerythritol, three(meth)acrylate pentaerythritol, ethoxylated three(meth)acrylate of trimethylolpropane, di(meth)acrylate, triethylene glycol di(meth)acrylate of ethylene glycol, dimethacrylate of tetraethyleneglycol, di(meth)acrylate of polyethylene glycol-600, 1,4-butanediol(meth)acrylate, glycerol dimethacrylate, di(meth)acrylate of pentaerythritol, (meth)acrylates of aminos; calironia oils, such as linseed oil, soybean oil and castor oil (meth)acre shall amides, maleimide, vinyl acetate, vinylcaprolactam, politely and simple vinyl ethers. Under the notation (meth)acrylate, you should understand the acrylate and/or methacrylate.

In particular, ground-based paint contains a compound with at least one isocyanate and at least one (meth)acrylate group. This isocyanate groups react with water with the formation of urethane groups. May is also the reaction with the carboxyl end groups of polyamide, which creates a strong connection, in particular covalent bond with the (co)polyamide. However, the exact reaction mechanism is not yet clarified. Curing dirt paint by the reaction of two different types of reactive groups, hereinafter also referred to as "dual-cure" (dual cure).

Used in the dirt paint oligomers or prepolymers are, in particular, resins with acrylate functional group, as epoxyacrylate, polyurethanacrylate and complex preferability modified (meth)acrylate, epoxy resins, modified (meth)acrylate polyesters, modified (meth)acrylate urethanes/polyurethanes, modified (meth)acrylate ethers, modified (meth)acrylate polybutadienes, (meth)acrylates of aromatic acids, modified (meth)acrylate acrylic oligomers and polymers from which SocialEngine with hydroxyalkylated esters of propionic acid.

Radical-curable dirt paint has a viscosity of from 0.2 to 0.7 PA·s, preferably about 0.3 PA·S.

Curing radicals under the action of UV printing ink contains monomers, oligomers and/or prepolymers, as well as pigments and at least one photoinitiator. Radical-curable UV printing ink has a viscosity of from 1.0 to 3.0 PA·s, preferably from 1.5 to 2.5 PA·S.

Further, the object of the invention is a single or multi-layer film based on (co)polyamide or with an outer layer based on (co)polyamide, which has a print radically curable inks, characterized in that the printing ink deposited on the layer of the radical-curable dirt paint, which is in the same molecule contains:

a) at least one group that can form a bond with the surface of the (co)polyamide, in particular by reaction of (poly)condensation, and

b) at least a group with ethylene unsaturation, which can join-initiated radical polyaddition reaction.

The term (co)polyamide in connection with the present invention should be understood polyamide, copolyamide, block copolymers with polyamide and/or copolyamid blocks, and any mixtures thereof. Reactive compound in the dirt paint preferably clicks is not covalent bonds with the surface (co)polyamide.

Dirt paint is applied to the containing (co)polyamide surface with a very thin layer. Preferably the proportion of the layer is at most 2.0 g/m2especially preferably 1.0 g/m2or less. For this ground the paint should be of relatively low viscosity. It is preferably from 0.2 to 0.7 PA·s, particularly preferably about 0.3 PA·C. the Desired viscosity can be achieved by adding reactive diluents, such as low viscosity monomers with a radical-polymerized olefinic double bonds, such as diacrylate tripropyleneglycol (TPGDA), diacrylate dipropyleneglycol (DPGDA), hexanediamine (HDDA) or triacrylate of trimethylolpropane (TMPTA). In principle, the viscosity can also be reduced by adulteration (non-reactive) organic solvent. However, there is an extra stage of drying, and application of soil paint can no longer hold in the production line. Therefore, the preferred ground paints that do not contain solvents. In any case, dirt paint and printing ink contains no water.

The layer of dirt paint almost colorless. Therefore, in order to control the print quality, earth-based paint, it is advisable contains another, invisible to the naked eye marking substance, such as a fluorescent pigment.

Oba is but dirt paint is applied on the entire surface. However, in principle, can also be applied in a dirt paint on the image, only those areas that later must be printed radically curable.

In addition, ground-based paint contains at least one photoinitiator, which can initiate radical polymerization of the ethylene-unsaturated monomers. Such initiators are well known. These include, for example, methyl ethyl ketone, acetophenone, dialkoxybenzene, benzaldehyde, benzophenone, 4-aminobenzophenone, simple antoinettelouis ether, dibenzosuberone, fluoren-9-he indan-1-he and thioxanthen-9-he, α-aminoacetophenone, also with the polymer structure, alkylbenzenesulfonate, hydroxyalkylated, polymeric derivatives of benzophenone and polymeric derivatives of aminobenzoate. Photoinitiator must have a low vapor pressure, can not be formed by irradiation of any unwanted by-products and not to paint the cured layer of soil colors. The effect of photoinitiators can be improved coinitiators. The percentage of all initiators (including coinitiator) suitable up to 10 wt.%, based on the weight of monomers.

The irradiation is usually carried out by UV radiation, however, in principle, also applicable electronic rays. To obtain sufficient crosslinking, is usually sufficient exposure time less than 2 s, before occhialino less than 1 C.

Radically curable ink print on opportunities immediately after irradiation. In several areas of the print (usually 3 to 6) is applied, as a rule, the radical-curable inks of different colors. It is advisable to radically curable inks do not contain solvent. The seal obtained with the radical-curable printing ink, has significantly less odor than obtained with cation-curable printing ink.

In any case, you cannot mix the ground paint printed paint and then irradiated. This standing in the basis of the invention the problem can not be resolved. Then the seal was not sufficiently fixed on the surface of the shell. Printing ink should be applied as soon as possible, i.e. in a matter of seconds or minutes after exposure of the layer of soil colors. In this case, is achieved particularly good adhesion of the print to a layer of soil colors. It is assumed that then a layer of dirt paint still contains radicals, which can react with the polymerizable compounds with the olefinic unsaturation in the composition of the printing ink. On the contrary, if applied in printing ink only after some time, that is, for example, in a few days, the adhesion of the print to a layer of dirt paint will be sufficient.

Radical-curable printing ink content is t, as dirt paint, at least one photoinitiator. Photoinitiator in printing ink may be identical or different from photoinitiators in the dirt paint. Photoinitiator in the printing ink must be capable of forming radicals that initiate polyprionidae monomers with ethylene-unsaturated bonds.

Radical otvergala UV printing ink contains monomers, oligomers and/or prepolymers having able to polymerization of olefinic double bonds, photoinitiator, dyes or pigments, if necessary, a binder. Preferably the ink contains no solvent. It is advisable to have a viscosity of from 1.0 to 3.0 PA·s, preferably from 1.5 to 2.5 PA·S.

One frequent variant of realization of the film seal is tubular film, in particular seamless tubular film. Blown film is, in particular, a wrapper for food products, in particular artificial sausage casings.

Thus, the object of the invention is also a method of obtaining a film print, which includes stages:

(a) obtaining a single - or multilayer film, which has a surface for printing consists mainly of (co)polyamides;

(b) if necessary, pre-treatment of the film surface by corona discharge;

(c) nonsenical on the surface of the film by means of radical-curable dirt paint dual-cured;

(d) curing dirt paint UV radiation and/or electron beams, forming a cured layer of dirt paints;

(e) printing the radical-curable UV printing ink;

(f) curing the printed ink by irradiation with ultraviolet light, forming a cured print, and

(g) optionally, one or multiple repetition of steps (e) and (f).

The film preferably is tubular, in particular seamless tubular film. Printing it is usually way flexographic printing, and the printing speed can be higher than 100 m/min, preferably above 120 m/min and particularly preferably above 140 m/min

As you know, different polyamides or copolyamids absorb up to 10 wt.% water by its weight. Before printing method according to the invention the surface of the (co)polyamide is not necessary to pre-dry. Water is usually contained in the film or film layer based (co)polyamides, turned out to be even advantageous for the purposes of the present invention.

The layer of soil colors and colorful layers resistant to ice, water and steam at temperatures from -20 to +115°C. Full migration from a casing of the seal is determined by extraction with water, according to the European standard EN 1186-5, or olive oil, according to the standard EN 1186-4, in accordance with the European ant is the instructions for migration 97/48/EC and 85/572/EEC (test conditions: 4 h/100°C, then within 10 days at 40°C). When this extraction is carried out only on the inside. It was found that these conditions can be extracted less than 10 mg / DM2film printing, i.e. the prescribed limits are not exceeded.

Having the seal film according to the invention may also be tubular. In this case, it is suitable as a wrapper for food products such as artificial sausage casings. Sausage casings when heated in water to about 80°C usually find a shrinkage of less than 20% in the longitudinal and transverse direction. When such thermal shrinkage of the film according to the invention does not damage the print, which is a problem in the known shells.

1. The system of printing inks for printing on films made in the form of membranes for food, with the surface-side printing based on (co)polyamide containing radical-curable paint and dirt, at least one radically curable under the action of UV printing ink, which forms a practically colorless layer of soil colors,
moreover, ground-based paint includes a reactive compound which is one molecule contains:
a) at least one group that can form a bond with the (co)polyamide surface; and
b) less than the least one group with ethylene unsaturation, which can join-initiated radical polyaddition reaction.

2. The system of printing inks according to claim 1, wherein the reactive compound is a monomer, oligomer and/or prepolymer.

3. The system of printing inks according to claim 1 or 2, characterized in that the group that can form a bond with the surface of the (co)polyamide is an isocyanate group.

4. The system of printing inks according to claim 1 or 2, characterized in that the group with ethylene unsaturation is a (meth)acrylate group.

5. The system of printing inks according to claim 1 or 2, characterized in that the reactive compound is a low viscosity monomer with a radical polymerizable olefinic double bonds, preferably di(meth)acrylate of tripropyleneglycol, di(meth)acrylate of dipropyleneglycol, di(meth)acrylate of hexandiol or three(meth)acrylate of trimethylolpropane.

6. The system of printing inks according to claim 1 or 2, characterized in that the radical-curable UV printing ink contains monomers, oligomers and/or prepolymers, as well as pigments and at least one photoinitiator.

7. The system of printing inks according to claim 1 or 2, characterized in that the radical-curable dirt paint has a viscosity of from 0.2 to 0.7 PA·s, preferably about 3 PA·S.

8. The system of printing inks according to claim 1 or 2, characterized in that the radical-curable UV printing ink has a viscosity of from 1.0 to 3.0 PA·s, preferably from 1.5 to 2.5 PA·S.

9. Single or multi-layer film made in the form of casings for food products, based on (co)polyamide or with an outer layer based on (co)polyamide, which is applied to the printing of the radical-curable printing ink, wherein the printing ink is printed on the layer of the radical-curable dirt paint, which forms a practically colorless layer of soil colors,
moreover, ground-based paint contains a reactive compound which is in the same molecule contains:
a) at least one group that can form a bond with the surface of the (co)polyamide, and
b) at least one group with ethylene unsaturation, which can join-initiated radical polyaddition reaction.

10. The film seal according to claim 9, wherein the reactive compound is a monomer, oligomer and/or prepolymer.

11. The film seal according to claim 9 or 10, characterized in that the group that can form a bond with the surface of the (co)polyamide is an isocyanate group.

12. The film seal according to claim 9 or 10, characterized in that the group with ethylene unsaturation which is a (meth)acrylate group.

13. The film seal according to claim 9 or 10, characterized in that the radical-curable UV printing ink contains monomers, oligomers and/or prepolymers, as well as pigments and at least one photoinitiator.

14. Film with printing on one or more PP-13, characterized in that it is tubular film, preferably seamless.

15. Film printing on 14, characterized in that it is a wrapper for food products, preferably artificial sausage casings.

16. Film printing on 14, characterized in that the layer of dirt in the paint and the paint layer (layers) are resistant to ice, water and steam at temperatures from -20 to 115°C.

17. Film printing on 14, characterized in that the layer of dirt in the paint and the paint layer (layers) are resistant to thermal shrinkage of the film in the longitudinal and/or transverse direction up to 20%.

18. Film printing on item 15, characterized in that a complete migration, measured according to EN 1186-5 with water as a model liquid according to EN 1186-4 with olive oil as a model fluid, on the inside of the shell with the seal after the exposure time to 4 h at 100°C and 10 days at 40°C. is less than 10 mg/DM2.

19. A method of obtaining a film with printing, made in the form of casings for food products, kiuchumi stage:
(a) obtaining a single - or multilayer films with surface-based (co)polyamide
(b) if necessary, a preliminary surface treatment by corona discharge;
(c) a coating film of the radical-curable with primer containing compound with at least one group that can form a bond with the surface of the (co)polyamide, and at least one group with ethylene unsaturation, which can join-initiated radical polyaddition reaction, and at least one photoinitiator;
(d) curing dirt paint water by UV radiation and/or electron beams, forming a cured layer of dirt paints;
(e) applying radical-curable printing inks immediately after irradiation dirt paints;
(f) curing printing inks water by UV radiation, forming a cured print and
(g) optionally, one or multiple repetition of steps (e) and (f), and the radical-curable dirt paint forms a practically colorless layer of soil colors.

20. The method according to claim 19, characterized in that used ground-based paint, which contains at least one reactive diluent.

21. The method according to claim 20, characterized in that the reactive diluent used low viscosity m is a non-radically-polymerizable olefinic double bonds, preferably tripropyleneglycol, dipropylenetriamine, hexaniacinate or trimethylolpropane.

22. The method according to claim 19, characterized in that it uses ground-based paint with a viscosity of from 0.2 to 0.7 PA·s, preferably about 0.3 PA·S.

23. The method according to claim 19, characterized in that dirt paint is applied on the film with a specific gravity of at most 2 g/m2preferably a maximum of 1 g/m2.

24. The method according to claim 19, characterized in that the print is applied on the film by the way flexographic printing.

25. The method according to claim 19, characterized in that the used radical-curable printing ink with a viscosity of from 1.0 to 3.0 PA·s, preferably from 1.5 to 2.5 PA·S.

26. The method according to claim 19, characterized in that the printing speed is more than 100 m/min, preferably greater than 120 m/min and particularly preferably more than 140 m/min

27. The method according to claim 19, characterized in that the printing is applied on the bag, preferably seamless film.



 

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18 cl, 2 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention can be used in producing pigments and/or filler materials for paper, paint and plastic. The composite contains particles of an inorganic and/or organic pigment and/or filler having equivalent diameter of 0.2-100 mcm, coated at least partially with a composition containing calcium carbonate particles having equivalent diameter less than 200 nm, and binder based on copolymers containing monomers in form of one or more dicarboxylic acids and one or more monomers from a group comprising diamines, triamines, dialkanolamines or trialkanolamines. Particles of the inorganic pigment and/or filler are selected from talc, mica or mixtures thereof. Particles of the organic pigment and/or filler are selected from polyethylene, polypropylene, polyethylene terephthalate or polystyrene. To obtain the composite, particles of the pigment and/or filler are mixed with a calcium carbonate composition, mainly in form of an aqueous suspension, and binder is added and the mixture is homogenised. In another version, the binder can be added to particles of the pigment and/or filler or to the calcium carbonate composition. Calcium carbonate is ground using ball mills, jet mills, burr mills or combination thereof cyclones and sieves.

EFFECT: obtained composites have high opacity, whiteness and lustre, high capacity for printing and resistance to segregation.

57 cl, 11 dwg, 4 ex

FIELD: chemistry.

SUBSTANCE: paint with thermo-, fire-protective properties contains (wt %): binder based on acrylic (co)polymers and/or silicone resins and organosoluble polyurethanes - (20-40), filler in form of a mineral component - (10-30), antipyrene additive - (10-20), modifying additive in form of ceramic and/or glass microspheres with diameter of 20-150 mcm -(10-30) and an organic solvent - the rest. The paint composition additionally contains bentonite powder, intercalated with cobalt Co2+ ions and/or cerium Ce3+ ions in amount of 3-7 wt %.

EFFECT: invention increases stability of the formed protective paint coating to thermal-oxidative reactions, improves environmental safety, fire-resistance of the protective coating and endows said coating with bactericidal properties.

7 cl, 2 dwg, 1 tbl

FIELD: coating production.

SUBSTANCE: invention is referred to silane-based coating production method. One or several silanes are condensed with diol or polyol, then a solvent is added laced with the reagent consisting of Lewis acids or Lewis bases. The coating material derived upon that is applied to the base coat and solidified. The silanes are selected out of 3-isocyanatopropyltrimecoxysilane and isocyanatopropyltriethoxysilane which are inorganically bound in advance in the amount of no more than 1%. Water ratio in the reaction is no more than 1%. Alcohols, acetates or simple ethers are added as solvents. Delustering agents, wetting dispersers, antifoam agents, waxes, biocides, preservatives or coloring pigments are further added. The coating is applied to the base coat by hydrochemical method, particularly, by sputtering, dipping, spray flow, rolling-up, spreading, impressing, flinging, doctor knife, as well as vacuum deposition. After being applied the coating material is solidified at the temperature from the ambient one to 1200°C. The base coat consists of metal, plastic, ceramics, lacquer, fabric, textile, natural substances, such as wood or leather, glass, mineral substances or composite materials.

EFFECT: mar-proof, anticorrosion, easily cleared, fingermark-free, antireflective, non-weep, scale-protective, diffuse-barrier, radiation-protective, or as self-cleaning, antibacterial, antimicrobic, tribological or hydrophobic coating.

16 cl, 4 ex

FIELD: construction.

SUBSTANCE: adhesive composition includes methyl methacrylate and benzoyl peroxide. The adhesive composition additionally contains triethanolamine, epoxy resin and a marshallite filler. Using the adhesive composition makes it possible to considerably increase the depth of porous material impregnation and to improve evenness of composition hardening in concrete. The adhesive composition may be used as a protective anticorrosion coating, in repair of various concrete structures from filling small cracks to puttying large defects, and also as a filling polymer composition for porous materials.

EFFECT: increased protection of concrete surfaces.

2 tbl, 7 ex

FIELD: construction.

SUBSTANCE: adhesive composition includes methyl methacrylate and benzoyl peroxide. The adhesive composition additionally contains triethanolamine, epoxy resin and a marshallite filler. Using the adhesive composition makes it possible to considerably increase the depth of porous material impregnation and to improve evenness of composition hardening in concrete. The adhesive composition may be used as a protective anticorrosion coating, in repair of various concrete structures from filling small cracks to puttying large defects, and also as a filling polymer composition for porous materials.

EFFECT: increased protection of concrete surfaces.

2 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing (meth)acrylic esters (F) based on alcohols having at least one carbon-carbon triple bond, characterised by that at least one alcohol having at least one carbon-carbon triple bond of formula (1) where R1 denotes hydrogen, alkyl having 1-18 carbon atoms; alkyl having 2-18 carbon atoms, aryl having 6-12 carbon atoms, cycloalkyl having 5-12 carbon atoms, interrupted, if necessary, by one or more oxygen and/or sulphur atoms and/or one or more substituted or unsubstituted amino groups, or a 5-6-member heterocycl having oxygen, nitrogen and/or sulphur atoms, wherein said residues can be substituted with aryl, alkyl, aryloxy, alkyloxy, heteroatoms/or heterocycles, respectively, and R2 denotes alkylene having 1-20 carbon atoms, cycloalkylene having 5-12 carbon atoms, arylene having 6-12 carbon atoms, or alkylene having 2-20 carbon atoms interrupted by one or more oxygen and/or sulphur atoms and/or one or more substituted or unsubstituted amino groups and/or one or more cycloalkyl groups, -(CO)-, -O(CO)O, -(NH)(CO)O-, -O(CO)(NH)-, -O(CO)- or -(CO)O, where the names of the residues can be replaced with aryl, alkyl, aryloxy, alkyloxy, heteroatoms and/or heterocycles respectively, n is a whole number from 0 to 3, preferably from 0 to 2 and more preferably from 1 to 2 and X; for each i=0 to n can be independently selected from a group comprising -CH2-CH2-O-, -CH2-CH(CH3)-O-, -CH(CH3)-CH2-O-, -CH2-C(CH3)2-O-, -C(CH3)2-CH2-O-, -CH2-CHVin-O-, -CHVin-CH2-O-, -CH2-CHPh-O- and -CHPh-CH2-O-, preferably from a group comprising -CH2-CH2-O-, -CH2-CH(CH3)-O- and -CH(CH3)-CH2-O-, and more preferably CH2-CH2-O-, where Ph denotes phenyl and Vin denotes vinyl, wherein the hydroxy groups of the alcohol are primary or secondary, esterified in the presence of at least one enzyme (E) with (meth)acrylic acid or re-esterified with at least one (meth)acrylic ester (D).

EFFECT: use of the present method enables to obtain esters of an acid based on alcohols which have carbon-carbon triple bonds with good output and low colour indices.

5 cl, 3 ex

Road marking paint // 2425076

FIELD: chemistry.

SUBSTANCE: road marking paint contains acrylic film-forming agent in form of a copolymer of n-butylmethacrylate with glycidylmethacrylate, calcite as filler, chloroparaffin CP-470 as plasticiser, toluene and ethyl acetate as an organic solvent, titanium dioxide as a pigment, an organic montmorillonite derivative Bentone SD-2 as a thickener, a dispersant in form of a mixture of natural phospholipids Soya lecithin, an anti-sedimentation agent in form of 20% solution of an organic compound in xylene M-P-A - 2000X, with the given ratio of components.

EFFECT: paint has high wear resistance of the film while retaining the rest of the characteristics.

2 tbl, 10 ex

FIELD: printing.

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

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

16 cl, 1 dwg, 4 tbl

FIELD: textiles and paper.

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

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

16 cl, 2 dwg, 2 tbl, 2 ex

FIELD: chemistry.

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

EFFECT: improved biodecomposition properties.

13 cl, 6 ex

FIELD: chemistry.

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

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

20 cl

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

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

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

1 tbl, 2 ex

FIELD: dyes.

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

EFFECT: improved properties of dye, improved preparing method.

14 cl, 6 ex

FIELD: 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: polymer materials.

SUBSTANCE: polyurethane resin is a product of reaction of at least one diisocyanate component and isocyanate-reactive components having first group of at least one polyol, second group of at least one polyol, and third group of at least one polyol, at least one amine, and, additionally, reaction-stopping agent, all polyols of the first group having average molecular mass between 1000 and 10000 g/mole, those of second group having average molecular mass between above 10000 and 20000 g/mole, and those of third group having average molecular mass equal to or higher than 800 g/mole. Ratio of diisocyanate component to isocyanate-reactive components is selected such that all isocyanate groups are present as products of reaction with isocyanate-reactive functional groups. Resin is used as film-forming binder in coating compositions, in particular in printing inks for printing on polyolefin substrates. Printing ink is preferably used for manufacturing printed layered articles.

EFFECT: increased gluing ability and heat resistance of ink laid on plastic substrate.

41 cl, 2 tbl, 12 ex

The invention relates to the field of compositions for coating, namely fluorescent stamp mastics for the application of texts or images on solid media, preferably pulp and paper, and can be used when drawing text and/or images special stamp mastic, preferably in the form of seals, for the protection of paper-based information from a fake
The invention relates to the field of compositions for coating, namely fluorescent stamp mastics for the application of texts or images on solid media, preferably pulp and paper, and can be used when drawing text and/or images special stamp mastic is preferably in the form of seals for the protection of paper-based information from a fake

FIELD: food industry.

SUBSTANCE: invention relates to food industry. The casing contains a tubular base on the outer surface whereof at least two longitudinal elements and crosswise elements crossing the latter are positioned. The crosswise elements are extended over the longitudinal elements and bonded to the tubular base at their intercrossing places using glue.

EFFECT: invention allows to expand the array of technical means used during sausage products manufacture.

11 cl, 3 dwg

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