Polyurethane resin and a method for preparation thereof, coating composition containing polyurethane resin, and use of polyurethane resin for printing on plastic substances

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 technical field

This invention relates to a polyurethane resin, the coating composition containing the specified polyurethane resin; to use the specified polyurethane resin for printing on plastic substrates, to a method for producing polyurethane resin and method for producing a layered product printed image on it.

Prior art

The polyurethane resin used as a binder in the compositions of the coating solvent for the plastic films and in the production of laminated products coated with the image. Layered products are products formed from multiple layers, and in which - depending on the destination of the final product - each layer consists of the same material or different materials. The preferred materials are paper, wood, textile, metal or plastic film. In the field of packaging food products layered products mainly made from plastic or metal films, in particular of metallic films, or from a combination of both. A film material is chosen so that the layered product can be subjected to sterilization processes without compromising the quality of the film and/or layered products. Another Avenue is the property of the layered product is they provide prints or images generally satisfactory appearance from the viewpoint of gloss or color stability. Layered products are usually manufactured in any combination of two or more layers by using adhesive or by coating extrusion method without glue. Regardless of the production method: imprint or, in General, any image that does not need to be printed, can be applied to one or both of the layer before applying the next layer (Roempp Lexikon, Lacke und Druckfarben, ed. U. Zoll, Georg Thieme Verlag, Stuttgart, New York 1998, p.214 and 318).

The coating compositions for laminated products, which are mostly in the form of printing ink must meet high standards. Resin, which is a film forming component of the composition should provide a dried layer with the desired strength of adhesion both to the underneath substrate and glue, or extruded layer. According to another requirement: the resin should ensure that the dried layer stability during and after sterilization processes and/or process in boiling water, even for a long period of time (e.g., during cooking). In addition, the dried layer should have a resistance to clumping and have stability at the time of sealing the layered product (e.g., in the production of bags). With the Tav - in the form of ink - must have print properties as applied to flexographic and gravure printing, which are usually used for printing on plastic films. Thus, the resin should allow the printing ink to be consistent-liquid, quick drying and soluble in esters and alcohols, in particular ethanol.

The document EP-604890 discloses inks for printing on the layered products) based on polyurethane resin. This polyurethane resin is a reaction product having a high molecular weight polyol as one compound with a molecular weight of from 3000 to 10000; having a low molecular weight polyol as one compound with a molecular weight less than 200, organic diisocyanate, extension chain and, optionally, the agent terminates the reaction. Polyol as one compound is chosen such that all high molecular weight polyol as one connection and a low molecular weight polyol as one connection had an average molecular weight in the range of values between 1500 and 2700, with the isocyanate index in the diisocyanate over a 2.0, and the nitrogen content in the polyurethane resin derived from the isocyanate groups of the diisocyanate, the values from 1.3 to 1,95 wt.%.

Since the printed and dried layers obtained paint according to EP-604890, in most cases possess n is mportant bond strength, therefore, the initial prikleivalos layers underneath basis, i.e. prikleivalos within the first 30 seconds after drying, bad. No initial prikleevaetsja results in at least partial transfer of the printed layer to the back side of the substrate/film to which is applied a layer, the retention time on the rollers or feet. Another disadvantage sheets/layers created by the paint according to EP 604890, - there is no resistance, in particular in conjunction extruded polypropylene or complex polyester. This circumstance is the cause of the damage to the edges of the layers during heat treatment of the layered product. In addition, ink is poorly compatible with alcohols as solvents used in flexographic printing. All these shortcomings are mainly due to the low characteristics of the polyurethane resin.

The objective of the invention is to eliminate these disadvantages of the prior art.

In particular, the objective of the invention is to provide a polyurethane resin, used as film-forming binders in coating compositions. The compositions of the coating must conform to the production - in its widest sense, any kind of dried layer on the plastic film and/or layered products. Polyurethane solidline to provide a dry layer of a good initial prikleivalos, in particular such that the layer is not damaged during storage and subsequent processing of the substrate/film, and during finishing of the layered product. The resin should also reduce the likelihood of delamination when sealing a plastic film or a layered product; it must be heat-resistant and soluble in alcohols and ether complex.

Another objective of this invention is to provide a method of producing the specified polyurethane resin.

Another objective of this invention is to provide printing inks for plastic substrates and laminated products in which it is printed and dried layers originally glued well to the substrate and in which the paint is pechatayuschiy processes flexographic and gravure printing.

This task is solved by the features of independent claims.

In particular, they are resolved through the application of polyurethane resin which is the reaction product of at least one diisocyanate and components having isocyanate reactive functional groups; these components contain the first group, at least one polyol, a second group of at least one polyol and the third group, at least one polyol and optionally at least one amine and the termination reaction of the agent; when the eat all the polyols mentioned first group have an average molecular weight in the range from 1000 to 10000 g/mol; all of the polyols mentioned second group have an average molecular weight of more than 10,000 to 20,000 g/mol; and all the polyols specified in the third group have an average molecular weight equal to or less than 800 g/mol; and the ratio of the equivalent weights of the diisocyanate and the components having isocyanate reactive functional groups is chosen so that essentially all of the isocyanate groups of the diisocyanate are present as a reaction product with one of the isocyanate reactive functional groups. This means that the free, unreacted isocyanate groups remains.

Polyurethane resin get first due to the reaction mixture containing the first group, at least one polyol and a second group of at least one polyol with at least one diisocyanate to the first isocyanate ragged prepolymer; and all the polyols mentioned first group have an average molecular weight in the range from 1000 to 10000 g/mol; and all the polyols mentioned second group have an average molecular weight in the range of values from 10000 to 20000 g/mol; and the ratio of the equivalent weights of the diisocyanate and the aggregate of the polyols of the first and second groups is from of 3.6:1 to 2.3:1; and, secondly, due to the response of the specified first isocyanate of orphanage of the prepolymer with the third group, at least one polyol, at the same time all the polyols specified in the third group have an average molecular weight equal to or less than 800 g/mol, up to a saturated polyurethane resin.

According to a preferred implementation: the first isocyanate ragged the prepolymer reacts with the specified third group of the polyol to the second isocyanate ragged prepolymer, and at the third stage, the specified second prepolymer reacting at least one diamine and, optionally, with choppy agent, up to a saturated polyurethane resin. The terms “rich” in this case means that the polyurethane resin has no remaining free unreacted isocyanate.

According to a preferred implementation of the present invention, the average molecular weight polyols mentioned second group has values from 10500 to 18,000 g/mol, and more preferably between 11000 and 16000 g/mol. The average molecular weight polyols mentioned first group preferably has a value of from 1500 to 8500 g/mol, and more preferably from 2000 to 8000 g/mol. The average molecular weight of the polyols of the third group is preferably equal to or less than 500 g/mol, and more preferably: equal to or less than 400 g/mol.

Polyurethane resin in accordance with this invention has an average molecular mA is su from 20000 to 80000 g/mol, preferably from 45,000 to 65,000 g/mol, and soluble in organic solvents including alcohols such as ethanol and ethyl acetate.

According to a preferred implementation: oreanization polyurethane resin according to this invention ranges from 8 to 15%.

The favorable properties of the polyurethane resin in relation to its binding properties in coatings can be affected by the number of relations is equivalent to the mass between the reagents. It should be noted that all of the following relations are implemented, developed to meet various required properties of the resin.

The ratio of equivalent weights of the diisocyanate and the components having isocyanate reactive functional groups is preferably in the range from 0.95:1 to 1.2:1, and more preferably from 1:1 to 1.1:1.

The ratio of equivalent weights of the diisocyanate and the aggregate of the polyols of the first and second groups is from 3.6:1 to 2.3:1, preferably 3:1.

It is assumed that, in particular, the polyols of the second group provide for polyurethane those binding qualities necessary for a strong initial prikleevaetsja, in particular in relation to the films of these apolar hydrocarbons as polypropylene. The ratio of the equivalent weight of the polyols of the first group and polyols of the second group predpochtite is) is from 1.5:1 to 9:1, more preferably from 3:1 to 8:1, and most preferably 5:1 to 6:1. But for some applications it is preferable to use a smaller amount of polyols of the second group. Therefore, according to another preferred implementation of the present invention: the ratio of the equivalent weight of the polyols of the first group and polyols of the second group is preferably from 50:1 to 60:1.

The ratio of the equivalent mass of the sum of the polyols of the first, second groups and polyols of the third group is from 0.9:1 to 1.2:1.

The ratio of equivalent weights of the diisocyanate and the amine is from 3.1:1 to 4.7:1, preferably of 3.3:1 to 3.7:1, and more preferably of 3.6:1.

The ratio of the equivalent mass of the sum of the polyols of the first, second, and third groups of amines ranges from 3.8:1 to 1.7:1; preferably is 2.1:1, and more preferably is 2.4:1.

The preferred average molecular weight of the sum of the polyols of the first, second and third groups is weight of from 3000 to 5000 g/mol, preferably from 3000 to 4000 g/mol.

According to a preferred implementation: the diisocyanates are selected from the group consisting of isophorondiisocyanate (IPDI), 4,4'-diisocyanatobutane (DFM), hexamethylenediisocyanate (GMDC), dicyclohexylmethane and colordistance. In particular, IFDI used either individually or in a mixture in the ratio of 1:1 with DFM. In another prepact the positive implementation used even polyisocyanate resin.

As the components having isocyanate reactive functional groups, use only those components that contain hydroxyl groups and/or amino groups. Although the aminoalcohols (compounds containing hydroxyl and amino groups) are not excluded from this invention, but are preferred pure components, i.e. components that have either a hydroxyl or amino group as the only isocyanate reactive functional groups.

The polyols of the first group preferably selected from the group consisting of dihydroxy - and trihydroxy-polyether polyols and complex oligopyrroles with a hydroxyl number in the range from 12 to 56 mg KOH/g

In a preferred embodiment, the polyols of the second group are selected from the group consisting of dihydroxy-epicrealm.

The polyols of the third group are selected from the group consisting of such Monomeric diols, as neopentylglycol, hexanediol or 1,4-butanediol, dihydroxy-oligoarticular, complex apically, solid ketone resins having the preferred hydroxyl number of at least 280 mg KOH/g but not more than 500 mg KOH/g In the preferred embodiment, the solid ketone resin is gidrirovannoe-condensed product of formaldehyde and aliphatic and/or aromatic ketone. Complex oligoarticular preference is sustained fashion have a hydroxyl number at least 140 mg KOH/g Complex oligopyrroles preferably is adeptly polyol based on a complex of the polyester.

Polyoxyalkylene glycols are preferred dihydroxy-polyether polyols. Polypropylenglycol (BCP) proved to be the most appropriate polyoxyalkylene glycol in the synthesis of polyurethane resin according to this invention. Preferred dihydroxy-polyetherpolyols is a polyester-based polycaprolactone.

Particularly preferred is a polyurethane resin in which the polyols of the first, second and third groups choose only among polyoxyalkylene glycols. Good results were obtained by receiving the first polyol as a mixture of two polyoxyalkylene glycols, one of which has an average molecular weight of from 3500 to 4500 g/mol, and the other from 7500 to 8500 g/mol, and due to their mixing with polyoxyethyleneglycol with an average molecular weight from 11500 to 12500 g/mol as the polyol of the second group. The polyol of the third group is a mixture of polyoxyethyleneglycol with an average molecular weight of from 350 to 450 g/mol and a Monomeric diol, such as 1,4-butanediol. Thus obtained polyurethane resin has good characteristics as a binder in coatings (“type”). For type polyoxyalkylene Glick is whether the second and third group preferably chosen among polypropylenglycol.

Since the preferred synthesis for type-A, other preferred polyurethane resin obtained by substituting a mixture of polyoxyalkylene glycols in the first group, at least one complex oligopyrroles with a hydroxyl number of from 12 mg KOH/g to 56 mg KOH/g, thus preserving the polyols of the second and third groups are the same (type-In). The replacement of polyoxyethyleneglycol third group of at least one solid ketone resin gives a polyurethane resin with satisfactory characteristics (type-C) Preferred ketone resin with a hydroxyl number of about 325 mg KOH/g (DIN 53240) with a melting point of 110 to 120°C. Ketone resins preferably have a TC of 80 to 130°C.

At least one amine used in the synthesis of polyurethane resin according to this invention, are selected from amines having an average molecular weight of from 60 to 400 g/mol. At least one amine is a diamine. The diamine is preferably selected from the group 1.3-bis(aminoethyl)cyclohexane, m-Xylenediamine or ISOPHORONEDIAMINE. Isophorondiamine (EFDA) has a positive effect on the initial prikleivalos some plastic substrates.

Breaking agents are selected from the group consisting of monoethanolamine, such as di-, triethanolamine, ethanol, n-propanol, isopropanol, 1.4-butanediol.

This izaberete is s also includes the coating composition, containing an organic solvent and a polyurethane resin according to this invention as at least one film-forming binder. In a preferred embodiment, the coating composition is a printing ink for printing on plastic substrates for the manufacture of printed laminated products. And in the coating composition, and in 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 of alcohols and esters.

Polyurethane resin allows a convenient way to adjust the printing ink according to the needs of flexo and gravure printing. The paint is soluble in alcohols, such as ethanol, has a low viscosity, i.e. is liquid grease has a viscosity of preferably from 30 to 100 seconds in the Cup 4 at 23°or from 80 to 350 MPa/s at 23°C.

Depending on the chemical structure of the polyurethane resin and, therefore, the chemical nature of the reagents and their respective relationship relative to each other: printing ink can be adjusted according to the needs of different types of plastic substrates and/or methods of application. The layer made from the coating composition having a polyurethane see the Lu type a as a binder, has good initial prikleivaemaya to the polyolefin substrate; polyurethane type resin-In provides a dry layer a very good initial prikleivalos for a plastic substrate, although it can also be applied to the polyolefin substrate. The type is particularly suitable for metallized films.

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

- Molecular mass expressed in average molecular mass.

- Average molecular weight of the sum of the polyols of the first, second and third group is calculated using the following formula:

where Mwix- molecular weight polyol i in group x; x=1-3

wix=the mole fraction of polyol i in group x; x=1-3

The term “film-forming” is determined according to DIN 55945:1996-09. “Film-forming” is a General term for the transition of the coating layer from a liquid to a solid state. Film formation occurs due to physical drying and/or curing. Both processes take place simultaneously, or one after the other. Polyurethane resin according to the present invention is film-forming at standard conditions (25°C, min 40% relative humidity). Since the term “drying” refers to the technology used for drying the liquid layer,such as a furnace and the temperature, the term “curing” refers to the chemical processes in the resin during the curing process. The polyurethane according to this invention is a polyurethane massivemocha type. The term “initial prikleivalos” is defined as prikleivalos directly after drying and up to 30 seconds, with a maximum, after drying of the layer.

The term “drying” means substantially removing the solvent from the layer. This is one of the requirements of the hardening layer. Residual solvent in the layer is not more than 10 wt.% from the weight of the entire solvent. The dried layer is a layer thickness of from 4 to 6 MK, in particular 5 MK, after processing in the infrared furnace at a temperature of 70-80°within less than one minute. In the solid state layer has no stickiness. If the layer is thicker or thinner than either the oven temperature needs to increase/decrease or adjust the duration of the heat treatment.

The terms “layer” and “image” are used synonymous in all the description. Layers and images have views of the drawings, labels, printing on top (covering varnishes); and their value should not limit their shape, size and thickness.

In the context of the present invention: all technical terms are defined according Roempp Lexikon, ed. U.Zoll, Georg Thieme Verlag Stuttgart, 1998.

In addition to the chemical structure and molecular mass polyols and will complement the Sabbath.) amines, favorable properties of the polyurethane resin may depend on the synthesis. The preferred method of synthesis is: first, the reaction of the diisocyanate with the combination of polyols with relatively high average molecular weight; and then preferably should the subsequent stage, which is used polyols lower molecular weight and, optionally, the diamines. This sequence of stages provides the distribution of urethane groups in the polyurethane resin, and this, apparently, is conducive to improve the initial prikleevaetsja and resistance to clumping.

Therefore, this invention also includes a method of obtaining a saturated polyurethane resin, according to which:

a) to provide a mixture containing the first group, at least one polyol and a second group of at least one polyol; at the same time all the polyols mentioned first group have an average molecular weight in the range of values from 1000 to 10000 g/mol; preferably from 1500 to 8500 g/mol, and more preferably from 2000 to 8000 g/mol; and all the polyols mentioned second group have an average molecular weight of more than 10,000 to 20,000 g/mol; preferably in the range of values from 10500 to 18,000 g/mol; and more preferably from 11,000 to 16,000 g/mol; and

b) carry out the reaction of this mixture of step (a) at m is re, one diisocyanate; the ratio of the equivalent weights of the diisocyanate and the amount of the polyols of the first and second groups is from 3.6:1 to 2.3:1.

According to a preferred implementation of this method also includes the step C): provide a third group of at least one polyol, the polyol specified in the third group have an average molecular weight equal to or less than 800 g/mol; preferably equal to or less than 500 g/mol, and more preferably equal to or less than 400 g/mol; and carry out the reaction of the polyols mentioned third group with the reaction product of step b); and provide a response for the specified product of step (C) at least one diamine on stage d). The product of stage (C) can additionally react with at least one polyol specified in the third group and/or breaking agent.

The invention also includes a method of obtaining a laminated product with a printed image on it; however, this method includes the steps

a) providing printing ink containing at least one organic solvent and at least one polyurethane resin according to this invention as a film-forming binder, and

b) applying a layer on the first substrate by printing shows the printing ink, obtained in step a), in the process of flexographic and/or gravure printing, specified on the first substrate;

c) remove the specified solvent from the specified layer applied in step b), thereby drying and/or otorita specified layer;

d) applying adhesive to the layer obtained in step (C), and finishes the layered product by placing a second substrate on the adhesive.

The first and second substrates are preferably made of plastic, preferably of polyolefin plastics. The first and the second substrate may also have a different chemical structure, for example: complex polyester or polyamide.

In accordance with this invention: as an adhesive in this way you can use any normal without solvent adhesive, or the adhesive is solvent-based. Examples of adhesives that contain solvents used according to this invention, are the following: Adcote 545/CAT F and Morton 301A/350A, manufacturer: Rohm & Haas; Novacote 275A/CA12, manufacturer - Novacote Flexpack; and Henkel UK 364/UK 6800, manufacturer : Henkel. An example of the adhesive without solvent used according to this invention, is: Mor-free SK403/C83, manufacturer : Rohm & Haas.

Adhesives applied to the layer according to conventional methods, for example using a portable device coating. Before applying the glue without solvent preferably diluted with normal dilute the LEM, such as ethyl acetate. Preferably prepared solution containing 20 wt.% up to 80 wt.%; more preferably from 30 wt.% up to 60 wt.% glue without solvent.

When using adhesives, solvent based, it is preferable to apply the adhesive on the printed layer of the substrate, and then decorate the layered product by applying a second substrate to the adhesive. But in the case of the use of glue without solvent is more preferable to apply the specified adhesive to the unprinted substrate layer, and then decorate the layered product by applying a printed layer of the second substrate on the adhesive.

Therefore, this invention also includes a layered product, which is obtained described above. Of course, the layered product can also be obtained by extrusion of the second substrate on the first substrate on which is the dried layer. For this method, adhesive is not required.

If necessary, a paint composition in accordance with this invention may contain additional binding resins, such as cellulose resin, acrylic resin, polyvinyl chloride.

The invention also includes a polyurethane resin containing the reaction product isocyanate groups, at least one diisocyanate, and a hydroxyl group, at least one dihydroxy-polyetherpolyols with an average molecular what assay over 10000 to 20000 g/mol; preferably from 10500 to 18,000 g/mol; and more preferably from 11,000 and 16,000 g/mol; and also containing the reaction product isocyanate groups, at least one diisocyanate with a hydroxyl group, at least one polyol with an average molecular weight in the range from 1000 to 10000 g/mol; preferably from 1500 to 8500 g/mol; and more preferably from 2000 to 8000 g/mol, chosen from the group consisting of dihydroxy - or trihydroxy-polyether polyols; and also containing the product of the reaction of isocyanate group with a hydroxyl group, at least one polyol with an average molecular weight equal to or less 800 g/mol, preferably equal to or less than 500 g/mol; and more preferably equal to or less than 400 g/mol which is chosen from the group consisting of Monomeric diols, dihydroxy-polyether polyols and complex oligopyrroles having a hydroxyl number of 140 mg KOH/g

The specified polyurethane resin can also contain a reaction product isocyanate groups, at least one diisocyanate with the amino group of at least one diamine, preferably of isophorondiamine.

In this polyurethane resin is preferable ratio of the equivalent weights of the diisocyanate and the combination of polyols with an average molecular weight of more than 10,000 to 20,000, and from to 10000 is from 3.6:1 to 2.3:1; preferably 3:1.

The specified polyurethane resin is preferably used as a binder in printing inks, in particular for printing on plastic substrates.

Another preferred variant of the present invention is a polyurethane resin containing the reaction product of at least one diisocyanate; preferably a mixture of two diisocyanates, such as IPDI and DFM; and at least one polyetherpolyols; for example polypropylenglycol preferably with an average molecular weight of from 11,000 to 16,000 g/mol; and at least one polyol, preferably two polyols; most preferably two polyether polyols, such as polypropyleneglycol with an average molecular weight in the range of values from 1500 to 8500 g/mol, and at least one polyol with an average molecular weight, equal to or lower than 800 g/mol, and at least one amine, preferably at least one monoamine and one diamine, such as monoethanolamine, IFDA. The ratio of equivalent weights of the polyols of the first group and polyols of the second group is preferably from 50:1 to 60:1. Other relationship is preferably those listed above in relation to other polyurethane resins according to this invention.

More in detail this invention opisyvaet the camping below in the following examples.

The method of measuring the initial prikleevaetsja.

Smokeaway tape (10 cm, type 683, manufacturer - 3M) put under edinoobraznym pressure on the printed layer directly after drying of the layer and separated from the substrate directly after that. The number of printed stamp stuck to the tape, are classified on a scale from 0 to 5, where 0 means over 95% of the printed layer, adhered to the tape; 1 means more than 50% of the printed layer, adhered to the tape; 3 means less than 20% of the printed layer, adhered to the tape; 4 means less than 10% of the printed layer, adhered to the tape; and 5 means less than 2% of the printed layer stuck to the tape. The trial was conducted additionally, depending on the drying time of the printed layer.

Measurement of heat resistance.

Thermal stability is checked using device hot seal Otto Brugger HS/ET or Otto Brugger HSG-C996, which both have prepective clamps. The audit was conducted according to the method Guiline S03/GUI/0001 Method 503/A.

Total synthesis of polyurethane resin (Example 3, Table 1).

Pathology flask with two additional funnels, means for introducing gas, a stirrer and a thermometer is filled with a mixture of 35 g of ethyl acetate and 0.06 g of Irganox 1076. The mixture was kept at a temperature of 25°With a stirring speed of 60 rpm and a flow of nitrogen of 0.4 cubic meters/hour, the Temperature increase is up to 60° With the mixture of 2.54 g IPDI, 1,37 g Desmodur 2460M (DFM) and 0.04 g of DBTDL (catalyst), diluted to 0.04 g of ethyl acetate, added to the flask. The mixing speed was increased to 90 rpm In isocyanate add a mixture 7,88 g BCP 2000 and 26,48 g BCPs 12000 in 15 g of ethyl acetate for 10 minutes the Reaction is carried out at a temperature of 74°for 180-240 minutes In the second stage, the mixture of 0.57 g of BCP 400 and 0.15 g of 1.4-butanediol is added slowly into the solution of the prepolymer of the first stage; the reaction is performed for 30 min before adding a third stage of 0.67 g of ISOPHORONEDIAMINE when the stirring speed of 120 Rev/min. the Reaction is carried out for a further 15 minutes In the fourth stage 0.17 g of 1,4-butanediol is added to the solution of the prepolymer obtained in the third step, to increase the molecular weight of the prepolymer. After 60-180 min reaction time added 0.18 g of monoethanolamine, and the reaction is further carried out for 30 min before adding 10 g of ethanol as the fifth and last step.

The NCO value was determined after each stage, and increase the molecular weight of the polyurethane during synthesis observed by measuring the gel permeation chromatography (Waters 410 and 510; column Lichrogel PS 4000/40/20, calibration polypropylenglycol 400-2000-4000-8200-12200-16000-20000).

Characteristics of polyurethane:

Mr:47000

Solids content: 40%

Viscosity: 2000-4000 MPa s/25°

Nitrogen, %: 1,19

The degree is realizatsii: 11,9

The average molecular mass of all polyols of the first, second and third phases: 3360 g/mol.

Examples 1-12 are given in Table 1 (Synthesis according to the General Synthesis).

The ink composition containing a polyurethane resin according to examples 1-12 Table I

Diluted varnish was prepared by mixing the following ingredients for 20 minutes:

Polyurethane binder - 86 parts

Alcohol - 9.5 parts

Waxes 3.3 parts

Protivovspenivayushchie additives - part 1,2

The final paint was prepared by mixing the following ingredients for 20 minutes:

WHITE/WHITE PAINT

Thin lacquer - 30 parts

Nitrocellulose white paste - 45 parts

Alcohol 15 parts

The ethyl acetate 10 parts

BLUE/BLUE PAINT

Thin lacquer - 30 parts

Nitrocellulose blue paste - 48 pieces

Alcohol and 12 parts

The ethyl acetate 10 parts

Table 2 gives the results of tests of paint compositions containing polyurethane resin of one of examples 1-12 Table 1.

Initial prikleivalos, the heat resistance and the strength of the lamination/delamination tested on substrates of different chemical nature and compared with the corresponding results of printing ink prepared according to the document EP 604890.

Use the following commercially available paint:

for the blue/C what she paints LAMIUHEKO; for white/white paint LAMIHALL - manufacturer of both: S INX Corp. Japan.

We used the following substrates:

Name of productThe chemical natureManufacturer
MB 400Jointly extruded doubly oriented polypropyleneMobil
200 MBjointly extruded doubly oriented polypropylene; simple biaxially oriented transparent polypropylene filmMobil
Terphane 10.10/1200Complex polyester, treated by corona dischargeToray Plastic
ORAPolyamideDu pont Nemour
Melinex 813Complex polyesterDu pont Nemour

Initial prikleivalos and the heat resistance was tested on a layer of printing ink in relation to the underneath substrate. For testing the lamination/delamination of the bond strength was tested on a layer of printing ink between two plastic films. The opposite substrate for all evaluated substrates was plastic film of low density.

Tested: the imprint of white paint as the only layer between the two plastic layers (indicated by b is small), the imprint of blue paint as the only layer between the two films (indicated in blue), and the overlay layer of blue and white paint between the two films (indicated as 200%).

Method of obtaining the layered material is a method of laminating based glue (glue: Mor-free SK403/C83 and Novacote 275/CA 12). Printed sample of a layered product of a width of 15 mm was placed between two clamps (dynamometer type Lhomargy). The sample was removed, and the substrate is separated from the opposite substrate. The bond strength (g/15 mm) and stratification check the layered product was evaluated at a speed of 200 mm/min. Strength is expressed as a combination of numerical values and characters. The numeric value indicates the grams required to separate layered product of a width of 15 mm and at a speed dynamometer 200 mm/min the higher the value, the stronger the relationship. The letters indicate the type of separation relative to the layer of printing ink:

T: transfer 100% of the paint layer (from the substrate to the opposite substrate).

R: the splitting of the ink layer (between the substrate and the opposite substrate).

Z: stable value for the bond strength is missing

R: gap/gap one of the two films of layered items.

1. Polyurethane resin which is the reaction product of at least one diisocyanate and isocyanate reactive components, which contain the first group, at least one polyol, a second group of at least one polyol and the third group, at least one polyol and, optionally, at least one amine and stopping the reaction agent, all of the polyols mentioned first group have an average molecular weight in the range of values from 1000 to 10000 g/mol, wherein all polyols of the specified second group have an average molecular weight in the range of values over 10000 to 20000 g/mol; all polyols specified in the third group have an average molecular weight equal to or less than 800 g/mol, and the ratio of the equivalent weights of the diisocyanate and the isocyanate reactive components is chosen such that essentially all of the isocyanate groups of the diisocyanate are present as the reaction product with one of these isocyanate reactive functional groups.

2. Polyurethane resin according to claim 1, characterized in that the ratio of equivalent weights of the diisocyanate and the aggregate of the polyols of the first and second groups is from 3.6:1 to 2.3:1, and preferably is 3:1.

3. Polyurethane resin obtained by reacting a mixture containing the first group, at least one polyol and the second group, at least one polyol with at least one diisocyanate to the first isocyanates ragged prepolymer; wherein all polyols of the specified first group have an average molecular weight in the range of values of 1000 to 10000 g/mol; all the polyols mentioned second group have an average molecular weight in the range of values over 10000 - 20000, and the ratio of the equivalent weights of the diisocyanate and the aggregate of the polyols of the first and second groups is 3.6:1 - 2,3:1; in the second step by reacting a first isocyanate ragged prepolymer with the third group, at least one polyol; at the same time all the polyols of the third group have an average molecular weight equal to or less than 800 g/mol, up to a saturated polyurethane resin.

4. Polyurethane resin according to claim 1, wherein the first isocyanate ragged the prepolymer reacts with the third group of the polyol to the second isocyanate ragged prepolymer and in the third group of the second prepolymer reacting at least one diamine and, optionally, with breaking agent to the saturated polyurethane resin.

5. Polyurethane resin according to claim 1, characterized in that the polyols of the second group have the t average molecular weight in the range of values 10500 - 18000 g/mol, more preferably 11000 - 16000 g/mol.

6. Polyurethane resin according to claim 1, characterized in that the ratio of equivalent weights of the diisocyanate and the components having isocyanate reactive functional groups is 0.95:1 to 1.2:1.

7. Polyurethane resin according to claim 1, characterized in that the ratio of equivalent weights of the polyols of the first group and polyols of the second group is 1.5:1 to 9:1, preferably 3:1 to 8:1, more preferably 5:1 to 6:1.

8. Polyurethane resin according to claim 1, characterized in that the ratio of equivalent weights of the polyols of the first group and polyols of the second group of 50:1 to 60:1.

9. Polyurethane resin according to claim 1, characterized in that the ratio of the equivalent mass of the sum of the polyols of the first group, polyols of the second group and polyols of the third group is 0.9:1 to 1.2:1.

10. Polyurethane resin according to claim 1, characterized in that the ratio of equivalent weights of the diisocyanate and the amine is 3.1:1 to 4.7:1, preferably of 3.3:1 to 3.7:1, more preferably of 3.6:1.

11. Polyurethane resin according to claim 1, characterized in that the ratio of the equivalent weight of the sum of the polyols of the first, second, and third groups of amines is 3.8:1 to 1.7:1, preferably about 2.2:1 and 2.7:1, more preferably of 2.4:1.

12. Polyurethane resin according to claim 1, characterized in that the polyols of the first group are selected from the group consisting of dihydroxy-and t is hydroxy-polyether polyols with a hydroxyl number 12 - 56 mg KOH/g

13. Polyurethane resin according to claim 1, characterized in that the polyols of the second group are selected from the group consisting of dihydroxyphenylpropionic.

14. Polyurethane resin according to claim 1, characterized in that the polyols of the third group are selected from the group consisting of Monomeric diols, dihydroxyphenylpropionic, complex oligopyrroles and solid ketone resin; and a hydroxyl number of solid ketone resin is preferably from 280 mg KOH/g to 500 mg KOH/g, a hydroxyl number of complex oligoarticular is at least 140 mg KOH/g

15. Polyurethane resin according to claim 1, characterized in that dihydroxyisopropyl selected from the group consisting of polyoxyethyleneglycol, preferably of polypropylenglycol and polyester-based caprolactone.

16. Polyurethane resin according to claim 1, characterized in that at least one amine is a diamine, preferably selected from the group consisting of ISOPHORONEDIAMINE, m-xylocaine, 1,3-bis(aminoethyl)cyclohexane.

17. Polyurethane resin according to claim 1, characterized in that the average molecular weight of the sum of the polyols of the first, second and third groups has values in the range 3000 - 5000 g/mol, preferably 3300 - 4000 g/mol.

18. Polyurethane resin according to claim 3, wherein the first isocyanate ragged the prepolymer reacts with the tre is ia group of the polyol to the second isocyanate ragged prepolymer and in the third group of the second prepolymer reacts at least one diamine and optionally with breaking agent to the saturated polyurethane resin.

19. Polyurethane resin according to claim 3, characterized in that the polyols of the second group have an average molecular weight in the range of values 10500 - 18000 g/mol, more preferably 11000 - 16000 g/mol.

20. Polyurethane resin according to claim 3, characterized in that the ratio of equivalent weights of the diisocyanate and the components having isocyanate reactive functional groups is 0.95:1 to 1.2:1.

21. Polyurethane resin according to claim 3, characterized in that the ratio of equivalent weights of the polyols of the first group and polyols of the second group is 1.5:1 to 9:1, preferably 3:1 to 8:1, more preferably 5:1 to 6:1.

22. Polyurethane resin according to claim 3, characterized in that the ratio of equivalent weights of the polyols of the first group and polyols of the second group of 50:1 to 60:1.

23. Polyurethane resin according to claim 3, characterized in that the ratio of the equivalent mass of the sum of the polyols of the first group, polyols of the second group and polyols of the third group is 0.9:1 to 1.2:1.

24. Polyurethane resin according to claim 3, characterized in that the ratio of equivalent weights of the diisocyanate and the amine is 3.1:1 to 4.7:1, preferably of 3.3:1 to 3.7:1, more preferably of 3.6:1.

25. Polyurethane resin according to claim 3, characterized in that the ratio of the equivalent weight amounts of the polyols of the first, the second, third groups and amines is 3.8:1 to 1.7:1, preferably about 2.2:1 and 2.7:1, more preferably of 2.4:1.

26. Polyurethane resin according to claim 3, characterized in that the polyols of the first group are selected from the group consisting of dihydroxy - and trihydroxypyrimidine with a hydroxyl number 12 of 56 mg KOH/g

27. Polyurethane resin according to claim 3, characterized in that the polyols of the second group are selected from the group consisting of dihydroxyphenylpropionic.

28. Polyurethane resin according to claim 3, characterized in that the polyols of the third group are selected from the group consisting of Monomeric diols, dihydroxyphenylpropionic, complex oligopyrroles and solid ketone resin; and a hydroxyl number of solid ketone resin is preferably from 280 mg KOH/g to 500 mg KOH/g, a hydroxyl number of complex oligoarticular is at least 140 mg KOH/g

29. Polyurethane resin according to claim 3, characterized in that hydroxypropionic selected from the group consisting of polyoxyethyleneglycol, preferably of polypropylenglycol and polyester-based caprolactone.

30. Polyurethane resin according to claim 3, characterized in that at least one amine is a diamine, preferably selected from the group consisting of ISOPHORONEDIAMINE, m-xylocaine, 1,3-bis(aminoethyl)cyclohexane.

31. Polyurethane resin according to claim 3, great the rpm die, the average molecular weight of the sum of the polyols of the first, second and third groups has values in the range 3000 - 5000 g/mol, preferably 3300 - 4000 g/mol.

32. The coating composition, preferably printing ink containing an organic solvent and at least one polyurethane resin according to one of claims 1 to 17 as a film-forming binder.

33. The use of polyurethane resin, as claimed in claims 1 to 31 as at least one film-forming binders in inks for printing on plastic substrates, preferably polyolefin plastic substrate.

34. A method of obtaining a saturated polyurethane resin, characterized in that

a) provide a mixture containing the first group, at least one polyol and a second group of at least one polyol; at the same time all the polyols mentioned first group have an average molecular weight in the range of values from 1000 to 10000 g/mol; all the polyols mentioned second group have an average molecular weight of more than 10,000 to 20,000 g/mol;

b) carry out the reaction of this mixture of step (a) at least one diisocyanate; the ratio of the equivalent weights of the diisocyanate and the amount of the polyols of the first and second groups is 3,6:1 - 2,3:1;

c) provide third group, at least one the first polyol, all of the polyols mentioned third group have an average molecular weight equal to or less than 800 g/mol;

d) carry out the reaction of the polyols mentioned third group with the reaction product of stage b) to product a higher average molecular weight than the weight of the product of stage b);

e) carry out the specified reaction product of at least one diamine.

35. The way to obtain a layered product printed on it layer, characterized in that

a) to provide a coating composition, preferably printing ink, in accordance with p;

b) put a layer on the first substrate, preferably a plastic film, by printing the specified ink stage in the process flexographic and/or gravure printing;

c) dried and/or utverjdayut layer obtained in step b) by removing the solvent from the layer,

d) put glue on the dried and/or cured layer obtained in stage C), and obtain a layered product by applying at least a second substrate, preferably a plastic film on the glue.

36. Layered product obtained by the method according to p.

37. Polyurethane resin containing the reaction product isocyanate groups, at least one diisocyanate and hydroxyl groups, at least one of dihydroxypregna Iola with an average molecular weight of more than 10,000 to 20,000 g/mol; preferably 10500 - 18000 g/mol; more preferably 11000 - 16000 g/mol; also containing the reaction product isocyanate groups, at least one diisocyanate with a hydroxyl group, at least one polyol with an average molecular weight in the range 1000 to 10000 g/mol, chosen from the group consisting of dihydroxy - or trihydroxypyrimidine; also contains the product of the reaction of isocyanate group with a hydroxyl group, at least one polyol with an average molecular weight equal to or less 800 g/mol, chosen from the group consisting of Monomeric diols, dihydroxy-polyether polyols and complex oligopyrroles having a hydroxyl number of 140 mg KOH/g

38. Polyurethane resin according to clause 37, wherein the polyurethane resin contains the product of the reaction of isocyanate groups and amino groups, at least one diamine, preferably of isophorondiamine.

39. Polyurethane resin according to clause 37 or 38, characterized in that the ratio of equivalent weights of the diisocyanate and the aggregate polyols average molecular weight of more than 10,000 to 20,000 and from 1,000 to 10,000 is from 3.6:1 to 2.3:1, preferably 3:1.

40. Polyurethane resin containing the reaction product of at least one diisocyanate, preferably a mixture of two diisocyanates and, at IU is e, one complex oligoarticular with an average molecular weight preferably 11000 - 16000 g/mol and at least one polyol, preferably two polyols with an average molecular weight of 1500 to 8500 g/mol and at least one polyol with an average molecular weight equal to or less than 800 g/mol and at least one amine, preferably at least one monoamine and one diamine in the ratio of equivalent weights of the polyols of the first group of polyols and polyols of the second group is preferably from 50:1 to 60:1.

41. The use of polyurethane resin, as claimed in p-40, as at least one film-forming binder in a printing ink for printing on plastic substrates.



 

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FIELD: organic chemistry, in particular polyol composition for cold-cured polyurethane production.

SUBSTANCE: claimed composition contains (pts mass): polyethertriol or mixture of polyethertriol with molecular weight of 4500-6500 and average hydroxyl functionality of 3 - 100; ethylene glycol - 3.5-6.2; 1-4-butandiol - 3,5-8,0; triethylene diamine - 0.53-0.65; water - 0.25-0.50; organosilicate foam regulator - 0.002-0.004; and high boiling by-product from isoprene production based on alkyl- and oxyalkyl-substituted dioxacyclanes (e.g., 1,3-dioxane containing 1-4 mass % of hydroxyl groups) as organic filler - 2-100. Said filler may be used in mixture with oil plasticizer. Polyurethane obtained according to present method has Shore A hardness of 20-50, and is useful in automobile industry, and as material for gasket and sealing.

EFFECT: composition for production of polyurethane with increased hardness.

2 cl, 1 tbl, 3 ex

FIELD: organic chemistry, polymer materials.

SUBSTANCE: polyester-polyols are obtained by double metalcyanide catalyzed polyaddition of alkylenoxide to starting material containing active hydrogen atoms. Alkylenoxide is continuously fed into reactor during induction period while maintaining constant pressure in reactor.

EFFECT: method for polyester-polyol production with decreased induction time.

2 ex, 1 dwg

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6 ex, 1 dwg

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