Polyurethane resin, obtained from poly hydroxilated resins, method of obtaining it and its application

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

The technical field to which the invention relates.

The present invention relates to a polyurethane resin composition for coating, containing mentioned polyurethane resin, to the use of the above polyurethane resin for printing on substrates made of plastic, to a method for producing polyurethane resin and to a method for producing a laminate with printed when you print the image.

Prior art

Polyurethane resin binders are preferred for solvent-containing compositions for coating films of plastic and upon receipt of the laminates with printed image. Laminates are a multi-layer molded product, in which - in accordance with the requirements of the final product of each of the layers is either the same, or from different materials. The preferred materials are paper, wood, textile, metal and a film of plastic. In the field of food packaging laminates mainly made of a film of plastic or metal, in particular from DRI films, or a combination of both. The materials of the films chosen such that the laminate can be subjected to sterilization processes without compromising the quality of the film and/or laminate. As additional benefits l minute give applied when printing the prints or in General images, satisfactory appearance in terms of Shine and strength of color. In General, laminates receive or result of joining two or more layers using adhesives, or as a result do not use adhesives coating extrusion method. Regardless of the method of obtaining one or both of the layer before applying the next layer can be applied the resulting printed imprint, or in General any type of image that does not have to be applied when printing (Römpp Lexikon, Lacke und Druckfarben, ed. U. Zorll, George Thieme Verlag, Stuttgart, New York, 1998, p.214 and 318).

Compositions for coating laminates, which are mainly available in the form of printing ink must meet high standards. Resin as the film-forming part of the composition should allow to obtain a dried layer with the desired adhesive strength as compared to the substrate, and glue or extruded layer. As additional requirements put forward that the resin should give a dried layer resistance during and after the sterilization process and/or process in boiling water even for a long period of time (for example, during the preparation of food). In addition, the dried layer has a show is its resistance to adhesion and resistance during welding of the laminate (for example, in the manufacture of packages). It is necessary that the composition as ink could be applied in printing by means of flexographic and gravure printing, which are techniques commonly used for printing on films of plastic. Thus, the resin should give the possibility of obtaining ink, low viscosity, fast drying and soluble in esters and alcohols, in particular ethanol.

In the work of the EP-604890 described ink (printing laminates) - based polyurethane resin. Polyurethane resin is a reaction product of high molecular weight polyol as one compound with a molecular weight in the range from 3000 to 10,000, low molecular weight polyol as one compound with a molecular mass of less 200, organic diisocyanates connection, extension circuits and optional agent of chain termination reactions. Polyol as one compound is chosen such that the combination of high molecular pomolnogo compounds and low-molecular-weight polyol as one connection would have an average molecular weight in the range from 1500 to 2700, with isocyanate index of diisocyanate exceeded the 2.0, and the nitrogen content in the polyurethane resin derived from the isocyanate groups of the diisocyanate, would be in the range from 1.3 to 1,95 wt.%. Used only a hundred is the standard polyether polyols based on ethers, such as polyethylene glycol. In addition, the importance of the selected band of molecular mass polyol as one component emphasized by the fact that when using a polyol as one component with a lower molecular weight is obtained, the paint which has poor adhesion and adaptability to treatment by boiling or sterilization in the autoclave.

Despite the fact that with the prints obtained by printing, and dried layers obtained using paint from EP-604890, in most cases demonstrate the required strength of the adhesion, initial adhesion of the layers relative to the substrate, i.e. stickiness within the first 30 seconds after drying, is unsatisfactory. Insufficient initial adhesion results during storage in rolls or stacks, at least to the partial transfer of layers of prints on the reverse side of the substrate/film, which was coated with the layer. Another disadvantage of prints/layers obtained using paint from EP 604890, is their insufficient heat resistance, in particular in the case of joint extrusion of polypropylene and complex polyester. The latter fact results in the occurrence of lesions on the edges of the layers during heat treatment of the laminate. In addition to this the mu ink shows poor compatibility with alcohols, representing the solvent preferred for applications with flexographic printing. All these shortcomings are mainly determined unsatisfactory performance polyurethane resin.

Disclosure of the invention

The aim of the present invention was to obtain a polyurethane resin used as the film-forming binder in compositions for coating, showing good initial adhesion and good compatibility with alcohols, as well as good heat resistance, in particular showing good adhesion to specific substrates and which are more solid compared to conventional polyurethane resins, such that can be obtained in a very broad sense - any type of dried layers on the films and/or laminates of plastic, these layers are characterized by excellent initial adhesion, in particular such that the layer is not damaged during storage and subsequent processing of the substrate/film during final processing of the laminate, in particular such that a reduced risk of delamination during welding film or a laminate of plastic.

The above-mentioned purpose, in accordance with the present invention are achieved by the use of the polyurethane resin constituting PR is the product of the reaction, at least one diisocyanate and component group containing a functional group having reactivity towards isocyanates, these group of components includes:

a) the first group formed of one or more polyether polyols on the basis of simple esters, each of which has an average molecular weight in the range of from 400 to 12,000 g/mol,

b) a second group formed of one or several polyhydroxyalkanoate resins selected from the group consisting of solid ketone resins, ketone resins based on polyesters, Acrylonitrile copolymers, acrylic polyols, derivatives of rosin and decentralisamanagement resins,

c) optional third group, formed by one or more polyols, each of which has an average molecular weight equal to or less 800 g/mol, and

d) at least one amine and the agent of chain termination reactions,

where the ratio of the equivalent weights of the diisocyanate and components containing a functional group having reactivity towards isocyanates, chosen so that essentially all of the isocyanate groups of the diisocyanate was present in the form of the reaction product with one of these functional groups having reactivity with respect the structure to isocyanates.

Use polyhydroxyalkanoic resin as one component having reactivity towards isocyanates, allows to obtain a polyurethane resin, which are more solid in comparison with commonly used polyurethane resins and which exhibit good adhesion to specific substrates, such as devuono-oriented polypropylene (VOR).

In accordance with the present invention determine the ranges include the boundaries of these ranges. For example, the range of molecular masses of from 2000 to 3000 g/mol must also meet the inclusion of compounds differing average molecular weight equal to 2000 g/mol and 3000 g/mol.

The polyurethane resin of the present invention has a mass-average molecular weight in the range from 3000 to 80000 g/mol, preferably from 20000 to 80000 g/mol, more preferably from about 35,000 to 55,000 g/mol, and it is soluble in organic solvents, including alcohols such as ethanol, and ethyl acetate.

In a preferred embodiment, the implementation of the polyurethane resin of the present invention is characterized by the degree of Aryanization in the range from 10 to 60%, preferably from 10 to 20%.

At the appropriate properties of the polyurethane resin in terms of its quality as a binder in coatings, can exert the influence of a set of equivalent ratios of masses between the reagents. You must understand that all the ratios listed below in the present invention, are simply embodiments, adapted to comply with different requirements to the resin.

In accordance with a preferred implementation of the present invention, the ratio of the equivalent weights of the diisocyanate and the combination of polyether polyols based on ethers of the first group, polyhydroxyalkane resin from the second group and polyols of the third group is in the range from 3.6:1 to 1:1, preferably equal to 1.5:1.

In accordance with another preferred implementation of the present invention, the ratio of the equivalent weights of the diisocyanate and components containing a functional group having reactivity toward isocyanates, preferably is in the range from 0.8:1 to 1.2:1, more preferably from 0.95:1 to 1.2:1, and still more preferably from 1:1 to 1.1:1.

In accordance with another preferred implementation of the present invention, the ratio of the equivalent weights of the diisocyanate and the amine is in the range from 2:1 to 6:1, preferably in the range of from 3:1 to 6:1, and more preferably in the range of from 3:1 to 5:1.

In a preferred embodiment, the implementation of a diisocyanate selected from a group consisting of isophorone ocyanate (IPDI), 4,4'-diisocyanatobutane (MDI), hexamethylenediisocyanate (HMDI), dicyclohexylmethane and toluylene diisocyanate (TDI). In particular, IPDI used either individually or in a mixture with MDI, a composition of 1:1. In another preferred embodiment, the implementation may use even polyisocyanate resins. However, it should be understood that for the purposes of the present invention may use any diisocyanate, commonly used in the synthesis of polyurethane resins.

As component containing a functional group having reactivity towards isocyanates, use only those components that contain hydroxy and/or amino groups. Despite the fact that the aminoalcohols (compounds containing hydroxy and amino groups) are not excluded from the present invention, the preferred pure components, i.e. components that contain or hydroxy-or amino group as the sole functional groups having reactivity towards isocyanates.

The polyether polyols based on ethers of the first group are preferably selected from the group consisting of dihydroxy - and trihydroxypyrimidine on the basis of simple ethers having an average molecular weight in the range of from 400 to 12,000 g/mol, preferably from 400 to 10,000 g/mol, bol is e preferably from 1000 to 10000 g/mol, and even more preferably from 2000 to 6000 g/mol, for example, characterized by a hydroxyl number in the range from 18.7 to 56 mg KOH/g is preferable dihydroxypyrrolidine on the basis of simple esters are polyoxyethyleneglycol, such as polypropyleneglycol (BCP), or polytetrahydrofuran (poly(THF)). It is established that polypropylenglycol (BCPs) is the most appropriate polyoxyethyleneglycol in the synthesis of the polyurethane resin of the present invention. In addition, preferred as dihydroxyphenethylamine on the basis of simple esters simple polyester-based polycaprolactone. However, for the purposes of this invention, the monomers are also suitable polyols based triolo or polyols with an even higher functionality, such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, trimethylated or 1,2,3-butanetriol.

Polyhydroxyalkane resin from the second group are selected from the group consisting of solid ketone resins, ketone resins, resins based on polyesters, Acrylonitrile copolymers, acrylic polyols, derivatives of rosin and decentralisamanagement resins.

In accordance with the present invention the solid ketone resins preferably are characterized by a hydroxyl number of at least 100 mg KOH/g but not reviewsin 500 mg KOH/g In particular, the preferred solid ketone resin, which is a hydrogenated product of condensation of aromatic ketone and aldehyde, in particular hydrogenated product of the condensation of acetophenone and formaldehyde. Such resins are sold, for example, with the trade name of a synthetic resin SK in Hüls, and it is characterized by a hydroxyl number approximately equal to 325 mg KOH/g, However, in accordance with the present invention the preferred polyhydroxyalkane resin that is different from the solid ketone resins.

In accordance with the present invention ketone resins preferably are polyketone resin, for example allegedley resin, such as K-1717 NMR or-1728 sold in the company Lawter International Inc., condensation products of cyclohexanone, preferably characterized by a hydroxyl number in the range of 100-200 mg KOH/g, for example Laropol K80 sold by the company BASF, or condensation products of aliphatic ketone and formaldehyde, preferably characterized by a hydroxyl number lower than 100 mg KOH/g, such as synthetic resin vehicle sold by the company Degussa-Hüls.

In accordance with the present invention resin-based polyesters preferably represent unsaturated does not contain parts of styrene resins, preference is characterized by a sustained fashion hydroxyl number, lower than 100 mg KOH/g, such as Haftharz LTH sold in Hüls.

In accordance with the present invention acrylontrile copolymers preferably are hydroxyquinoline copolymers, preferably characterized by a hydroxyl number in the range from 50 to 150 mg KOH/g, such as NeoCryl B-850 sold by Zeneca.

In accordance with the present invention acrylic polyols are polyol as one of resin, preferably characterized by a hydroxyl number in the range from 100 to 200 mg KOH/g, such as Reactol 180 sold in the company Lawter International Inc.

In accordance with the present invention derivatives of rosin preferred are maleic or fumaric derivatives of rosin.

In accordance with the present invention decentralitralisation resins preferably are characterized by a hydroxyl number in the range from 100 to 200 mg KOH/g, such as Dertophene N 150 sold the company Les Pèrivès Rèsiniques & Terpèniques S.A.

The polyols of the third group is preferably selected from the group consisting of Monomeric diols, such as neopentylglycol, hexanediol or 1,4-butanediol, dihydroxyphenylpropionic on the basis of simple esters, such as polypropyleneglycol or polyether polyols based on esters. The polyether polyols n the basis of esters preferably are characterized by a hydroxyl number at least, equal to 140 mg KOH/g, Preferably polyetherpolyols-based ester is a polyol based adipinate complex polyester.

The amine used in the synthesis of the polyurethane resin of the present invention are selected from those which have an average molecular weight in the range from 60 to 400 g/mol. Preferably the amine is a diamine. The diamine is preferably chosen from the group formed by 1,3-bis(aminoethyl)cyclohexane, m-xradiation or ISOPHORONEDIAMINE. Isophorondiamine (ACCESSORIES>) favorable effect on the initial adhesion of the coating to a certain type of substrates from plastic.

Agents open circuit selected from the group consisting of monoethanolamine, such as mono-, di-, triethanolamine, ethanol, n-propanol, isopropanol, 1,4-butanediol.

In accordance with the present invention is preferred polyurethane resin which is a reaction product between at least one diisocyanate and the group of compounds having reactivity towards isocyanates, consisting at least of one or more polyether polyols on the basis of simple esters, each of which has an average molecular weight in the range from 400 to 10,000 g/mol, preferably from 1000 to 10000 g/mol, one or more polyhydroxylated what's resins, selected from the group consisting of ketone resins, resins based on polyesters, Acrylonitrile copolymers, acrylic polyols, derivatives of rosin and decentralisamanagement resins, optional third group, formed by one or more polyols, each of which has an average molecular weight equal to or less 800 g/mol, and at least one amine agent and the chain termination reaction, where the ratio of the equivalent weights of the diisocyanate and components containing a functional group having reactivity towards isocyanates, chosen so that essentially all of the isocyanate groups of the diisocyanate have in the quality of the reaction product with one of these functional groups having reactivity towards isocyanates.

Particularly preferred polyurethane resin is a reaction product between at least one diisocyanate, such as a mixture of IPDI and MDI with a composition of 1:1, and compounds having reactivity towards isocyanates, including polypropylenglycol (BCPs)with an average molecular weight of approximately 4000-4500 g/mol, synthetic resin SK as polyhydroxyalkanoic resin, 1,4-butanediol as a low-molecular polyol and one or the number of amine compounds, such as ACCESSORIES > and monoethanolamine.

Polyurethane resin corresponding to the present invention, it is possible to synthesize in a result

a) the reaction between the mixture containing the first group formed of one or more polyether polyols on the basis of simple esters, each of which has an average molecular weight in the range of from 400 to 12,000 g/mol, a second group formed of one or several polyhydroxyalkanoate resins selected from the group consisting of solid ketone resins, ketone resins, resins based on polyesters, Acrylonitrile copolymers, acrylic polyols, derivatives of rosin and decentralisamanagement resins, and optional third group, formed by one or more polyols, each of which has an average molecular weight equal to or less 800 g/mol, and at least one diisocyanate to obtain a prepolymer with terminal isocyanate groups, the ratio of the equivalent weights of the diisocyanate and the combination of polyether polyols based on ethers of the first group, polyhydroxyalkane resin from the second group and polyols of the third group is in the range from 3.6:1 to 1:1, and

b) the reaction between the prepolymer with terminal isocyanate groups and at least one diamine and

c)the reaction between the product, obtained in accordance with stage b), and the agent of an open circuit with getting saturated polyurethane resin.

"Rich" in this context means that the polyurethane resin essentially does not contain the remaining unreacted isocyanate groups.

The conditions under which the original substances react with each other, correspond to the standard methods of synthesis of polyurethane resins, and they are well known among specialists in the respective field.

The subsequent part of the present invention relates to compositions for coating containing an organic solvent and a polyurethane resin of the present invention as at least one film-forming binder. In a preferred embodiment, the implementation of the composition for coating is a printing ink that is used for carrying out printing on the substrates of plastic and to obtain laminates with prints applied when printing. As in compositions for coating and printing ink polyurethane resin can be used as the sole film-forming binder.

The solvent is chosen from the group of polar organic solvents, preferably from the group formed by alcohols and esters.

Polyurethane resin is doing in zmeinym simple adaptation of printing ink to the requirements of the ways flexographic and gravure printing. The paint is soluble in alcohols, such as ethanol, is characterized by low viscosity, thus, being of low viscosity having a viscosity preferably in the range of from 30 to 100 seconds in the pit 4 at 23°or from 80 to 350 MPa·s under 23°C.

Depending on the chemical structure of the polyurethane resin and, thus, the chemical nature of the reagents and the corresponding reciprocal ratio of their quantities of printing ink can be adapted to the requirements of various types of plastic substrates and/or methods of application.

In the context of the present invention provides the following definitions.

Molecular weights are expressed through the mass-average molecular weight.

The average molecular mass of all polyols of the first, second and third groups expect

i, x=3

∑(Mw_ix. w_ix)

i, x=1

Mw_ix= molecular weight polyol i in group x, where x=1-3,

w_ix= the mole fraction of polyol i in group x, where x=1-3.

The term "film formation" is defined in accordance with DIN 55945:1996-09. Film formation is a generic term for the transition of the coating layer from liquid to solid. Film formation occurs as a result of the drying and/or curing. Both methods are implemented simultaneously or one after the other. Polyurethane resin in the present invention is film-forming at standard conditions (25° With minimum relative humidity 40%). While the term "drying" is more related to the technology used for drying the liquid layer, such as baking ovens and temperatures, the term "curing" refers to the chemical processes inside the resin during the drying process. The polyurethane of the present invention relates to massively type.

"Initial adhesion" is defined as an adhesion directly after drying and a maximum of up to 30 seconds after drying of the layer.

"Drying" refers to substantially remove the solvent from the layer. The latter constitutes one of the necessary conditions to ensure that the layer became solid. The content of residual solvent in the layer does not exceed 10 wt.% based on the weight of the entire solvent. The dried layer is a layer with a thickness in the range of 4 to 6 μm, in particular 5 μm, after processing in the infrared furnace at a temperature of 70-80°within less than one minute. In the solid state layer does not tack-free. If the layer is thicker, or thinner, then either you need to increase/decrease the oven temperature, or properly should be adjusted duration of heat treatment.

"Layer" and "image" are used interchangeably throughout the description. Layers and images are displayed as images, is adesa, overprint (varnish), and their importance should not be limited to their shape, length and thickness.

In the context of the present invention, all technical terms should be defined in accordance with the work of the Römpp Lexikon, ed. U. ZolI, Georg Thieme Verlag Stuttgart, 1998.

The present invention further includes a method of producing a laminate having obtained when printing the image, while the above-mentioned method includes a step

a) receiving printing ink containing at least one organic solvent and at least one polyurethane resin of the present invention as at least one film-forming binder, and

b) applying a layer on the first substrate as a result of printing using the printing ink obtained in stage (a)according to the method of flexographic and/or gravure printing on said first substrate,

c) removal of the above-mentioned solvent of the above-mentioned layer deposited on a stage (b), thereby drying and/or otorita layer

d) applying the adhesive layer on the stage (s) and final processing of the laminate by applying an adhesive to the second substrate.

Preferably the first and second substrates are comprised of plastic material, preferably having a polyolefin nature. The first and second substrates may also have other chemical nature, such as the complex of polyester or polyamide.

In accordance with the present invention as an adhesive in this way you can use any ordinary adhesive containing no solvent or adhesive containing solvent. Examples of adhesives, solvent-based, used in accordance with the present invention, are Adcote 545/CAT F and Morton 301A/350A from the company Rohm & Haas, Novacote 275A/CA12 or Novacote 120 ASL/111B from the company Novacote Flexpack and Henkel UK 3640/UK 6800 from Henkel. An example of this solvent-free adhesive used in accordance with the present invention, is Morfree SK403/C83 from the company Rohm & Haas.

Adhesives applied on the layer in accordance with commonly used methods, for example by means of a manual installation for coating. Adhesives, solvent free, before applying preferably diluted using commonly used diluent such as ethyl acetate. Preferably thereby obtain a solution containing from 20 to 80 wt.%, more preferably from 30 to 60 wt.% adhesive, solvent free.

In the case of adhesives, solvent based, in accordance with the present invention is preferred to apply the aforementioned adhesive on the substrate layer obtained by printing the printout, and then to the final processing of the laminate by applying an adhesive to the second substra the and. However, in the case of glue, solvent free, it is more preferable to apply the aforementioned adhesive layer on the substrate, having obtained when printing of the print, and then perform the final processing of the laminate by applying an adhesive layer obtained by printing imprint of the second substrate.

Therefore, the subsequent part of the present invention relates to a laminate obtained by the method mentioned earlier in this document. Needless to say that the laminate can also be obtained by the method of extrusion of the second substrate on the first substrate having the dried layer. This method does not require the use of glue.

If necessary, the paint composition of the present invention may contain additional binding resins, such as cellulose resin, acrylic resin, polyvinyl chloride.

The present invention will be described in more detail using the following examples. Unless other specified, all percentages are wt.%. Eq denotes equivalents.

Total synthesis of polyurethane resin

In pathology flask, equipped with two nutrient craters, the device for introducing gas, a stirrer and a thermometer, was loaded a mixture of 60% ethyl acetate and 0.06% Irganox 1076. The mixture thermostatically at 25°when the stirring speed of 60 rpm and photocathode 0.4 m ³/hour. The temperature was increased to 60°and to the flask was added a mixture 6,59% (a 1.5 Eq) IPDI, 7,45% (a 1.5 Eq) of Desmodur 2460M (MDI) and 0.03% DBTDL (dilaurate dibutylamino) (catalyst), diluted in 0.03% of ethyl acetate. The mixing speed was increased to 90 rpm over a period of time with a duration of 10 minutes to a solution of the isocyanate was added to 77.77% (1 Eq) Acclaim 4200 (polypropylenglycol sold in the company Voeg). The reaction was carried out at a temperature of 74°C for 180 minutes. Then to the solution of prepolymer was slowly added to 3.64% (0,37 Eq) Reactol 180 and the reaction was carried out for 15-30 minutes. Then, if the stirring speed is 120 rpm was added 2.73 percent (0,84 Eq) of ISOPHORONEDIAMINE. The reaction was carried out for 15 more minutes. Then for another 15-30 minutes added 0,82% (0,47 Eq) of 1,4-butanediol. Then the solution of the prepolymer was added 1% (0,43 Eq) of monoethanolamine. At the end of the reaction time duration of 15 minutes for dilution was added 10% ethanol.

The resulting polyurethane resin was characterized by a dry matter content of 30%, a viscosity of 15 PZ at 25°and degree of Aryanization 15%.

NCO number was determined after each stage, and the increase in molecular weight of the polyurethane in the course of the synthesis was observed through measurement by GPC method (pump: Waters 515 HPLC, the sample injection: auto sampler, Waters 717 plus, detector: refractive index of Water 2414; speakers: styragel HR1 (100-5000), styragel HR4E (50-100000); polystyrene standard calibration: 381:478:2950:6520:9650:18600:43700:177000:387000).

The method of measuring the initial adhesion

On the layer obtained when printing print directly after drying the layer at a uniform pressure was applied self-adhesive tape (10 cm, type 683 from the 3M company) and immediately after that, she was detached from the substrate. The quantitative share of the print stuck to the tape, classified in a scale from 0 to 5 where 0 represents more than 95% of the layer of the print stuck to the tape, 1 indicates more than 50% of the layer of the print stuck to the tape 2 means less than 30% of the layer of the print stuck to the tape; 3 denotes less than 20% of the layer of the print stuck to the tape, 4 denotes less than 10% of the layer of the print stuck to the tape, and 5 corresponds to less than 2% of the layer of the print stuck to the tape. The results of the tests are additionally arranged depending on the time of drying the layer obtained when printing of the print.

The ink composition containing a polyurethane resin corresponding to the present invention

The technological composition of varnish based on polyurethane:

The composition of the white ink:

Composition blue ink:

Tests to determine the initial adhesion, heat resistance and strength of the layup/peeling was performed for substrates of different chemical nature and the results were compared with the corresponding results for typographs the oops paint, in a composition which includes a polyurethane resin, which is synthesized without the use of a hydrophilic water-soluble polyol as one component.

Used the following substrates:

Tests to determine the initial adhesion and heat resistance were carried out in the system layer of printing ink and substrate. In the test layering/peeling was determined by the strength of coupling in the system layer of ink between two plastic films. Protivostala for all used in the test substrates was film of low density polyethylene.

The tests were carried out for the obtained print print white paint as the only layer between two films of plastic (the designation "white"), obtained when printing imprint blue paint as the only layer between the two films (the designation "blue") and overlay layers of blue and white paint between the two films (the designation "200").

Method of obtaining a laminate is a method of laminating based on the use of glue. The sample laminate with printed when printing the print with a width of 15 mm was placed between two clamps (type dynamometer Lhomargy). The sample was stretched and the substrate was separated from protivostat. Adhesion strength (g/15 mm) and the type of exfoliation I used for testing of the laminate was evaluated at a speed of 200 mm/min, the adhesion Strength was expressed as a combination of numerical values and characters. The numerical value indicates the number of grams required to separate the laminate of a width of 15 mm at a speed dynamometer 200 mm/min, the higher the value, the greater the strength of the coupling.

The letters indicate the type of the fracture with respect to the layer of printing ink.

T: transfer 100% of the ink layer from the substrate to protivostat).

R.: separation of the ink layer (between the substrate and protivostala).

Z: the lack of consistent values for the strength of adhesion.

R: gap/gap one of the two laminate films.

1. Polyurethane resin, which is a product of a reaction between at least one diisocyanate and components containing a functional group having reactivity towards isocyanates, which has the following composition:

a) the first group, formed by one or several is likemy the polyether polyols based on ethers, each of which has an average molecular weight in the range of from 400 to 12,000 g/mol,

b) a second group formed of one or several polyhydroxyalkanoate resins selected from the group consisting of solid ketone resins, ketone resins, unsaturated does not contain links styrene resins based on polyesters characterized by a hydroxyl number lower than 100 mg KOH/g, acrylontrile copolymers, acrylic polyols, derivatives of rosin and decentralisamanagement resins,

c) optional third group, formed by one or more polyols, each of which has an average molecular weight equal to or less 800 g/mol, and which are selected from the group consisting of Monomeric diols, dihydroxyphenylpropionic on the basis of simple esters, polyether polyols based on esters, and

d) at least one amine and the agent of chain termination reactions,

where the ratio of the equivalent weights of the diisocyanate and components containing a functional group having reactivity towards isocyanates, chosen so that essentially all of the isocyanate groups of the diisocyanate was present in the form of the reaction product with one of these functional groups having reactivity towards isocyanates.

2. poliuretanowa resin according to claim 1, in which the ratio of the equivalent weights of the diisocyanate and the combination of polyether polyols based on ethers of the first group, polyhydroxyalkane resin from the second group and polyols of the third group is in the range from 3.6:1 to 1:1, preferably equal to 1.5:1.

3. Polyurethane resin according to any one of claim 1 or 2, in which the ratio of the equivalent weights of the diisocyanate and components containing a functional group having reactivity towards isocyanates, is in the range from 0.8:1 to 1.2:1, preferably from 0.95:1 to 1.2:1, more preferably from 1:1 to 1.1:1.

4. Polyurethane resin according to claim 1, in which the ratio of the equivalent weights of the diisocyanate and the amine is in the range from 2:1 to 6:1, preferably in the range of from 3:1 to 6:1, and more preferably in the range of from 3:1 to 5:1.

5. Polyurethane resin according to claim 1, in which the polyether polyols based on ethers of the first group have an average molecular weight in the range from 2000 to 6000 g/mol.

6. Polyurethane resin according to claim 5, in which the polyether polyols based on ethers of the first group are selected from the group consisting of dihydroxy - and trihydroxyacetophenone.

7. Polyurethane resin according to claim 6, in which dihydroxyphenethylamine on the basis of simple ethers are selected from the group consisting of polyoxyethyleneglycol, site is preferably of polypropylenglycol, or polytetrahydrofuran and caprolactone.

8. Polyurethane resin according to claim 1, in which a ketone resins are polyketone resin, for example, allegedley resins, condensation products of cyclohexanone, preferably characterized by a hydroxyl number in the range of 100-200 mg KOH/g, or condensation products of aliphatic ketone and formaldehyde, preferably characterized by a hydroxyl number lower than 100 mg KOH/g

9. Polyurethane resin according to claim 1, in which acrylontrile copolymers are hydroxyquinoline copolymers, preferably characterized by a hydroxyl number in the range from 50 to 150 mg KOH/g

10. Polyurethane resin according to claim 1 where the acrylic polyols are resin polyol as one characterized by a hydroxyl number in the range from 100 to 200 mg KOH/g

11. Polyurethane resin according to claim 1, in which decentralitralisation resins are characterized by a hydroxyl number in the range from 100 to 200 mg KOH/g

12. Polyurethane resin according to claim 1 in which the amine is a diamine, preferably selected from the group consisting of ISOPHORONEDIAMINE, m-xylocaine, or 1,3-bis(aminoethyl)cyclohexane.

13. A method of obtaining a polyurethane resin according to any one of claims 1 to 12, comprising the following stages:

a) the reaction between the mixture of sod is rzasa first group, formed one or more polyether polyols on the basis of simple esters, each of which has an average molecular weight in the range of from 400 to 12,000 g/mol, a second group formed of one or several polyhydroxyalkanoate resins selected from the group consisting of solid ketone resins, ketone resins, unsaturated does not contain links styrene resins based on polyesters characterized by a hydroxyl number lower than 100 mg KOH/g, acrylontrile copolymers, acrylic polyols, derivatives of rosin and decentralisamanagement resins, and at least one diisocyanate to obtain a prepolymer with terminal isocyanate groups

b) carrying out the second stage reaction between the prepolymer with terminal isocyanate groups and at least one diamine and

c) conducting at the third stage of the reaction between the product obtained in accordance with stage b), and the agent of an open circuit with getting saturated polyurethane resin.

14. The method according to item 13, in which the mixture further includes a third group is formed of one or more polyols, each of which has an average molecular weight equal to or less 800 g/mol, and which are selected from the group consisting of Monomeric diols, dihydroxyphenylpropionic based on the question what's of esters, the polyether polyols based on esters.

15. The method according to PP and 14, in which the ratio of the equivalent weights of the diisocyanate and the combination of polyether polyols based on ethers of the first group, polyhydroxyalkane resin from the second group and polyols of the third group is in the range from 3.6:1 to 1:1.

16. Polyurethane resin obtained by the method according to p-15.

17. Coating for application on a substrate of plastic, which represents preferably a printing ink containing a polar organic solvent and at least one polyurethane resin, as claimed in any one of claims 1 to 12, as a film-forming binder.

18. The polyurethane resin according to claims 1-12, as at least one film-forming binders in inks for carrying out printing on substrates made of plastic, preferably on a substrate of a polyolefin plastic.

19. A method of producing a laminate having a layer obtained by printing of a print, comprising the following stages:

a) receiving the applied coating, preferably printing ink, P16;

b) applying a layer on the first substrate, preferably a plastic film, as a result of printing using the ink from stage a) according to the method of flexographic and/or the chap who Oka printing;

c) removing solvent from the layer for drying and/or curing the aforementioned layer, obtained in stage b),

d) applying glue to the dried and/or cured layer obtained in stage C), and applying at least a second substrate, preferably a film of plastic, glue obtaining a laminate.

20. The laminate obtained by the method according to claim 19.