Solvent-free self-curing polyurethane dispersions

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing self-curing polyurethane dispersions, use thereof as coating agents, coating agents containing these self-curing aqueous dispersions, a method of coating substrates, as well as substrates treated with coating agents. The method of producing self-curing aqueous polyurethane dispersions involves the following steps: I. reacting al) polyisocyanate with a mixture of, a2) 2,2-bis(hydroxymethyl)alkanecarboxylic acid as an anionic hydrophilisation agent containing a group which is reactive towards isocyanate and, a3) at least one polyol component with average OH-functionality >1, wherein any mixture from a2) and a3), or component a1) k) contains at least one catalyst selected from a group consisting of tertiary amines, tin, zinc or bismuth compounds; II obtaining an OH-functional polyurethane without NCO-groups from step I, which then; III. a4) is mixed with a reactive blocking agent for isocyanate groups, selected from a group consisting of butanone oxime, diisopropylamine or tert-butylbenzylamine, 3,5-dimethylpyrazole, triazole, respectively, mixture thereof; IV. subsequent reaction of that mixture from step III with a5) one or more polyisocyanates selected from group a1), wherein these polyisocyanates are the same as or are different from al), and subsequent V. obtaining a physical mixture of OH-functional polyurethane without NCO-groups and a blocked polyisocyanate from step IV, after which after either; VI. acid groups of OH-functional polyurethane a6) are completely or partially deprotonated by adding a neutralising agent; VII. and the polyurethane obtained at step VI id dispersed in water, or step VII is carried out before step VI.

EFFECT: obtaining self-curing aqueous polyurethane dispersions containing negligible amounts of cosolvent.

14 cl, 1 tbl, 5 ex

 

The present invention relates to a method for self-curing polyurethane dispersions obtained in this way is self-curing aqueous dispersions, their use as a means to cover, including these self-curing water dispersion means for covering, the method of coating substrates, and the substrates subjected to the processing for coverage, including self-curing water dispersion.

In the last few years has increased the importance of water varnishes and funds to cover due to increasingly stringent guidelines regarding emissions released during the application of varnishes solvents. Though now in the case of many applications available aqueous lacquer systems, in most cases, they often contain originating from the process of obtaining significant amounts of co-solvents. In particular, is still unknown no depleted in co-solvent used from the aqueous phase means for coatings based on polyurethane, which sufficiently satisfy the high requirements of the practice in the case of a primary coating of cars.

In recent years, achieved further improvement in the case of one-component lacquers hot drying. In the application for a European patent A-1311571 describes smoote gaudiest polyurethane dispersion, derived from physical mixtures containing urethane groups and hydroxyl groups of the polyols and dehydrofreezing blocked, at least 50 equiv.% derivatives dimethylpyrazole polyisocyanates. These physical mixtures of polyol as one of the components and blocked polyisocyanates have a distinct technical in respect of varnishes advantages, however, have considerable disadvantages with regard to their get. First, according to the specified application blocked polyisocyanate component a in a separate reaction vessel, which means significant additional costs compared with the method, which is carried out in the same vessel. Secondly, due to the large viscosity blocked MDI in the form of a pure substance is indicated by the addition of solvents, as otherwise the dosage is impossible. For technical reasons in relation to the security of such solutions in vysokoletuchih solvents, such as acetone, cannot be stored or transported, so that in case of blocked polyisocyanates can be used exclusively volatile ingredients solvents. They inevitably remain in dipersio and lacquer compositions and are released only when using that, as a rule, is undesirable. Described in the application for the European the cue patent And 1311571 self-curing system hot drying contain from 4.8 wt.% to 11.3 wt.% co-solvents relative to the dispersion, this is too much for some applications systems for coating water-based.

Another disadvantage described in the application for a European patent A-1311571 method lies in the fact that the blocked polyisocyanates inevitably consistently can not dissolve in the solvent. Some of the blocking means is therefore not applicable.

The present invention therefore consists in obtaining self-curing aqueous polyurethane dispersion which does not contain any quantities or contains only very small amounts of co-solvent, so that can't happen no volatility co-solvent at the end-use.

This task is solved through the method of obtaining self-curing aqueous polyurethane dispersions comprising the following stages:

I. introduction in interaction

a1) MDI

with a mixture of,

A2) at least one containing reactive towards isocyanate group, anionic hydrophilizing funds with an average OH-functionality ≥1 and

A3) at least one polyol as one component with an average OH-functionality of >1,

either a mixture of A2) and A3), component a1)

K) contains at least one catalyst;

II. getting OH-functional and not containing NCO-groups is of olyurethane with stage I, then

III. A4) is mixed with a reactive blocking agent for isocyanate groups;

IV. subsequent introduction into the interaction of this mixture with stage III

A5) one or more polyisocyanates selected from group a1), and these polyisocyanates are the same as or different from a1), and then

V. obtaining physical mixture of OH-functional does not contain NCO groups of the polyurethane and blocked MDI with stage IV, then then either

VI. the acid groups of the OH-functional polyurethane

A6) fully or partially deprotonated by adding a neutralizing means

VII. and received at this stage, the polyurethane is dispersed in water

or stage VII is carried out until the stage VI.

Proposed according to the invention is advantageous when the stage VI is carried out until the stage VII.

Proposed according to the invention is advantageous when the stage VII is carried out until the stage VI.

Proposed according to the invention is advantageous when the blocking means according to stage III use of compounds selected from the group consisting of butanonoxime, Diisopropylamine and 3.5-dimethylpyrazole.

Proposed according to the invention is advantageous when with the adiya's II or stage III use up to 30 wt.% in terms of the polyurethane with stage II solvent or mixture of solvents, selected from the group consisting of acetone, methyl ethyl ketone and tetrahydrofuran, and mixtures thereof, which is then removed by distillation after stage VII.

The next subject of the present invention are self-curing aqueous polyurethane dispersion obtained by proposed according to the invention method.

Another object of the present invention is the application of the proposed according to the invention self-curing aqueous polyurethane dispersion to obtain funds to cover.

A further object of the present invention are funds to cover, including proposed according to the invention self-curing aqueous polyurethane dispersion.

Proposed according to the invention the means for covering is advantageous when it is chosen from the group consisting of paints, varnishes and adhesives.

A further object of the present invention is a method of coating substrates, and the proposed use according to the invention the means for covering.

Proposed according to the invention a method of applying a coating is advantageous when the car bodies or parts of vehicle bodies are coated using the proposed according to the invention the means for covering.

As the subject of us who Otsego of the invention is the substrate, containing coating, including proposed according to the invention the means for covering.

Proposed according to the invention, the substrate is pre-emptive, when he represents the entirety of the vehicle or the rear of a vehicle.

In the proposed according to the invention the dispersion ratio of the resulting blocked with a blocking means A4) isocyanate groups to reactive towards isocyanates with hydroxyl groups, select components from 0.2 to 5.0 to 1, preferably 0.4 to 2.0 to 1, particularly preferably 0.5 to 1.5 to 1.

The number of individual components establish so that you receive the following mass ratio of components a1)-A6):

a1): 3-25, preferably 6-18, particularly preferably, 7 to 14 mass parts;

A2): 0.3 to 8, preferably 1 to 6, particularly preferably, 2 to 5 mass parts;

A3): 40-85, preferably, 50 to 75, particularly preferably 60 to 70 mass parts;

A4): 1-20, preferably, 3-17, particularly preferably 4 to 10 mass parts;

A5): 3-25, preferably 5 to 20, particularly preferably 9 to 17 mass parts;

A6): 0.5 to 10, preferably 1 to 6, particularly preferably 2-4 mass parts;

to): 0.001 to 2, preferably from 0.005 to 0.1, particularly preferably from 0.01 to 0.08 mass parts.

These mass parts belong to the specified component is m without its share of water or possibly available solvents.

The amount of neutralizing means A6), in General, set so that the degree of neutralization is available in polyurethane with stage II carboxyl and/or sulfoxylate groups (molar ratio of amine used to the available acid groups) is at least 50%, preferably from 80% to 120%, particularly preferably from 95% to 105%. Neutralization can be made before, during or after the stage of dispersion (stage VII), respectively, of dissolution. However, it is preferable implementation of neutralization before adding water (up to stage VII).

In the case of component a1) can be used individually or in any mixtures with one another, all organic, with isocyanate groups of the compounds, however, preferably, aliphatic, cycloaliphatic, aromatic or heterocyclic polyisocyanates with an NCO-functionality ≥2, and insignificant, whether by vosganian or according to the methods without the use of phosgene.

Examples of such isocyanates are tetramethyldisilane, cyclohexane-1,3 - and -1,4-diisocyanate, hexamethylenediisocyanate (HDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl (isophorondiisocyanate, IPDI), Methylenebis(4-isocyanatobenzene), tetramethylethylenediamine (TMXDI), triisocyanate the national Academy of Sciences, toluenediisocyanate (TDI), difenilmetana-2,4'- and/or -4,4'-diisocyanate (MDI), triphenylmethane-4,4'-diisocyanate or naftilan-1,5-diisocyanate and any mixtures of such isocyanates.

Also well suited to produce from them the polyisocyanates with uretdione, carbodiimide, which is, aminoacidopathies, biuret, urethane, allophanate, oxidization or acylceramide structure, as well as the polyisocyanate prepolymers with an average NCO-functionality of >1, which are obtained by pre-reaction of a molar excess of one of the above polyisocyanates with organic substance which has at least two reactive towards isocyanate hydrogen atom in the molecule, for example, in the form of hydroxyl groups.

In the case of component a1) is preferably used compounds of the above type with a molecular weight of 140 g/mol to 1000 g/mol.

In the case of component a1) is particularly preferably used polyisocyanates or mixtures of polyisocyanates of the specified type with exceptionally alifaticheskii and/or cycloaliphatic bound isocyanate groups, in particular those based hexamethylenediisocyanate (HDI), isophoronediisocyanate (IPDI) and/or 4,4'-diisocyanatohexane.

Polyol as one component A2) preferably has an average OH-functionality is inost from 1 to 6, preferably, from 2 to 4, and srednecenovogo molecular weight of from 62 g/mol to 2500 g/mol, preferably from 62 g/mol to 1000 g/mol, particularly preferably from 62 g/mol to 500 g/mol, and includes containing acid functional group of the compounds having along with the acid functional group has at least one reactive towards isocyanate hydroxyl group.

In the case of these compounds it is mainly about having at least one, preferably one or two hydroxyl groups, carboxylic acids or salts such hydroxycarbonic acids. Suitable such acids are, for example, 2,2-bis(hydroxymethyl)alcancarao acid, as dimethyllysine acid, 2,2-dimethylolpropionic acid, 2,2-dimethylaniline acid or 2,2-dimethylamphetamine acid, dihydroxyethane acid, hydroxypivalic acid or mixture of such acids.

As component A5) is preferably used dimethylolpropionic acid and/or hydroxypivalic acid.

Particularly preferably, the component A2) comprises only such of the above compounds with acid functional group, in a highly preferred as component A2) used exclusively dimethylolpropionic to the slot.

Used in case A3) polyol as one component consists of

B1) 2-6-atomic alcohols with srednekislye molecular mass of from 62 g/mol to 300 g/mol, preferably from 62 g/mol to 182 g/mol, particularly preferably from 62 g/mol to 118 g/mol,

B2) polyols with an OH functionality ≥2 and with srednekislye molecular mass of from 300 g/mol to 5000 g/mol, preferably from 300 g/mol to 3000 g/mol, particularly preferably from 300 g/mol to 2000 g/mol,

and/or

B3) monofunctional linear polyether with srednekislye molecular mass of from 300 g/mol to 3000 g/mol, preferably from 300 g/mol to 2000 g/mol, particularly preferably from 300 g/mol to 1000 g/mol.

As polyols B1) use 2-6-atomic alcohols and/or mixtures thereof, which do not have any ester groups. Typical examples are ethanediol-1,2, propandiol-1,2 and -1,3, butanediol-1,4, -1,2 or -2,3, hexanediol-1,6, 1,4-dihydrocyclopenta, glycerin, trimethylacetyl, trimethylolpropane, pentaerythritol and sorbitol.

Preferred compounds in the case of B1) are 1,4 - or 1,3-butanediol, 1,6-hexanediol and/or trimethylolpropane.

Suitable polyols of component B2) are selected from the group consisting of polyethers, polyesters and/or polycarbonates. Component B2) preferably includes at least one containing complex is aeternae groups of the polyol with srednetsenovoj molecular weight of 350 g/mol to 4000 g/mol, preferably, from 350 g/mol to 2000 g/mol, particularly preferably from 350 g/mol to 1000 g/mol. The preferred average OH-functionality ranging from 2 to 4 hydroxyl groups per molecule.

Such containing ester groups of the polyols is in itself known preferability, which are synthesized from low molecular weight polyols and dicarboxylic acids. Suitable low molecular weight polyols for this purpose are, for example, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, trimethylolpropane, pentaerythritol or sorbitol. Suitable dicarboxylic acids are, for example, aromatic dicarboxylic acids as phthalic acid, isophthalic acid and terephthalic acid; cycloaliphatic dicarboxylic acids, as hexahydrophthalic acid, tetrahydrophtalic acid, andalternative acid and/or their anhydrides; and aliphatic dicarboxylic acids as succinic acid, glutaric acid, adipic acid, cork acid, azelaic acid, sabotinova acid and/or their anhydrides. For the synthesis of complex episodios preferably used aliphatic dicarboxylic acid.

As politicophobia in the case of component B2) is preferably used polycaprolactone with srednetsenovoj molecular weight of the 350 g/mol to 4000 g/mol, preferably, from 350 g/mol to 2000 g/mol, particularly preferably from 350 g/mol to 1000 g/mol. Get them in itself known by way of diol, triol or a mixture of diol to triol, for example, the above-mentioned sort of as an initiator and ε-caprolactone.

Preferred polycaprolactone obtained by polymerizationε-caprolactone when using 1,6-hexanediol as an initiator.

Especially preferred politicomilitary are those based on adipic acid, phthalic acid, isophthalic acid and tetrahydrophthalic acid as the acid component and 1,4 - or 1,3-butanediol, 1,6-hexanediol and/or trimethylolpropane as the alcohol component.

In the case of component B2) you can also use the simple (co)polyesters of ethylene oxide, propylene oxide and/or tetrahydrofuran. Preferred are polyethers with srednetsenovoj molecular weight of from 500 g/mol to 2000 g/mol, as oxides or polytetrahydrofuran.

Further, in the component B2) can also be included containing the hydroxyl group of the polycarbonate, as exenteration, or polyaminocarboxylic preferred srednetsenovoj molecular weight of from 400 g/mol to 4000 g/mol, particularly preferably from 400 g/mol to 2000 g/mol.

The prigoda is passed monofunctional simple linear polyester as component B3) are, for example, a simple (co)polyesters of ethylene oxide and/or propylene oxide. Preferred initiated monohydroxy alcohol simple polyalkyleneglycols with srednetsenovoj molecular weight of 350 g/mol to 2500 g/mol with a content of at least 70% ethylenoxide links. Particularly preferred such (co)polymers with more than 75% ethylenoxide links and srednetsenovoj molecular weight of from 300 g/mol to 2500 g/mol, preferably from 500 g/mol to 1000 g/mol. As molecules initiators for these polyethers preferably used monofunctional alcohols with 1 to 6 carbon atoms.

Used in the case of A4) of the blocking means is chosen from itself known locking means for isocyanate groups, and used the blocking means must have a higher reactivity in relation to isocyanate groups than the hydroxyl groups of the polyurethane. Examples of suitable blocking means are oximes, as butanonoxime, amines, as Diisopropylamine or tert-butylbenzylamine, 3,5-dimethylpyrazole, triazole, respectively, and their mixtures. Preferred are butanonoxime, Diisopropylamine, 3,5-dimethylpyrazole or mixtures thereof.

The reactivity of the blocking means with respect to isocyanate groups can be easily identified special the leaf in this area and refers to the temperature range from 0°C to 100°C, preferably, from 20°C to 60°C. Reactivity can be enhanced through well-known expert in the field of catalysts, which can also be systematically stronger to increase the reactivity of the blocking means than the reactivity of the alcohol groups of the polyol.

Used as A5) polyisocyanate component may consist of the same structural elements that are specified in the case of component a1). Components a1) and (A5) can be the same or different.

In the case of component A5) preferred polyisocyanate components, respectively, of their mixture with the isocyanate functionality in the range from 2 to 6, particularly preferably from 2.5 to 5 and, in the highest degree preferably from 3 to 4.5.

Example used as a component A6) neutralizing means are triethylamine, dimethylaminoethanol, dimethylcyclohexylamine, triethanolamine, methyldiethanolamine, diisopropanolamine, ethyldiethanolamine, diisopropylethylamine, N-methylmorpholine, 2-amino-2-methyl-1-propanol, ammonia, hydroxides like sodium hydroxide, or any mixture thereof. Preferred neutralizing means are tertiary amines like triethylamine, diisopropylethylamine and dimethylethanolamine, especially preferred is dimethylethanolamine.

The agreement is but a preferred form of execution proposed in the invention, a method of introducing reactive towards isocyanate components A2) and A3) and the catalyst to) and then mixed with polyisocyanate a1) according to stage I of the proposed in the invention method. Temperature range thus set is preferably from 50°C to 140°C. the Catalyst) may be added to any of the components a1), A2) or A3), or it can be added separately. The reaction according to stage I can be done in directionspublic in relation to isocyanate solvents, so-called co-solvents, the preferred implementation of this reaction stage I without co-solvents. After mixing components a), a1), A2) and A3) according to the stage I mix up until by IR spectroscopy no longer find any NCO-groups.

Get OH-functional and not containing NCO-groups of the polyurethane according to stage II, then in accordance with the preferred option dissolved in volatile miscible with water co-solvent with a boiling point below 85°C at a pressure of 1013 mbar, such as acetone, and then mixed with a blocking agent A4). Alternatively, also you can first admix the blocking agent to the polyurethane with stage II proposed according to the invention method, and then dissolving the resulting mixture in a solvent. The preferred solvent content in the mixture from stage II depends on its viscosity and is from 0 wt.% up to 60 wt.%, particularly preferably, from 5 wt.% up to 30 wt.%. The temperature of the mouth of nalivajut in the range from 0°C to 80°C, predpochtitelno, from 20°C to 50°C. Then add the polyisocyanate component A5) so that the temperature did not exceed 80°C. it is Preferable to maintain a temperature range from 20°C to 60°C during the addition and subsequent stirring. The mixture is stirred until until by IR spectroscopy no longer find any NCO-groups.

According to the preferred form of the acid groups of the polyurethane of the structural element A2) then fully or partially deprotonated using the base A6), followed by dispersion in water.

For dispersion in water solution of the polyurethane, if necessary, with a strong shift, in General, with the energy of mixing from 1 W/l up to 1000 kW/l or contribute to the water dispersion or the water dispersion admixed to the solution of the polyurethane. Preferably, water is added to the dissolved polyurethane.

At the end of the dispersion according to stage VII possible volatile solvent is removed by distillation. The distillation is preferably carried out in vacuum at temperatures from 20°C to 70°C, particularly preferably, from 30°C to 50°C. Vacuum set in the range of, preferably, from 50 mbar to 500 mbar, particularly preferably from 100 mbar to 200 mbar. You can octanal is to the desired temperature and then install required for distillation vacuum or Vice versa. According to highly preferred course of action first establish a vacuum in the range from 100 mbar to 200 mbar and then the dispersion is heated from room temperature to a temperature of 40°C. the Advantage of this way is insignificant fraction of solvent in the finished dispersion, which, as a rule, is lower than 0.5 wt.% relative dispersion.

Further, it is possible, but not preferable, to add others that are not removed by the distillation of the alcohol. They are used in such a way that they contain up to 4 wt.%, preferably, up to 2 wt.%, relative dispersion. Especially preferred is getting free from the co-solvent dispersions.

To accelerate the reaction stage I use at least one catalyst to)selected from the group consisting of tertiary amines, compounds of tin, zinc or bismuth, particularly preferred are triethylamine, 1,4-diazabicyclo[2,2,2]octane, diktat tin and dibutyltindilaurate highly preferred diktat tin, dibutyltindilaurate. This catalyst for polyurethane) accelerates the formation of urethane on stage II. According to the application for the European patent A-2006/005878 also use the above catalysts. However, in this case they are used as Katalizator the block at a later stage of the method.

Thus obtained according to the invention self-curing aqueous dispersions have a solids content as non-volatile components from 10 wt.% up to 70 wt.%, preferably, from 30 wt.% up to 55 wt.%, relative dispersion, determined by drying the film at a temperature of 100°C to constant weight.

Received on proposed according to the invention method variance as not containing free hydroxyl group of one-component systems hot drying can be used to obtain varnishes, inks and other compositions. Thus together, you can use conventional technology coating AIDS and additives as pigments, improving the filling means to prevent the formation of bubbles additives or catalysts. It is also possible mixture with other reactive against alcohol compounds, such as, for example, cross-linking of resins, such as melamine resins and/or urea resins, for additional crosslinking during hot drying.

The object of the present invention is also the application of the proposed self-curing according to the invention aqueous dispersions for producing paints, varnishes or adhesives, in particular for the primary coating of cars, as well as coating on tin cans and a wire helix.

These one-component water to cover, which include a proposed according to the invention self-curing water dispersion, it is possible to apply a single-layer or multi-layer on any heat-resistant substrates according to all any methods technology coating, as spraying, smearing, dipping, drenching, or using a roller or squeegee. Varnish film, in General, have a layer thickness in dry state of from 0.001 mm to 0.3 mm

Suitable substrates are, for example, metal, plastic, wood or glass. The curing of the varnish film takes place at a temperature in the range from 80°C to 260°C, preferably from 130°C to 240°C.

Water funds for one-component coating preferably suitable for the production of coatings and lakirovanie on the steel sheets, which, for example, are used for the manufacture of car bodies, machines, wood, barrels or containers. Especially preferred is the use for motor fillers and/or coating varnishes.

Examples

Desmodur®N 3300

Isocyanurate on the basis of hexamethylenediisocyanate, Bayer MaterialScience AG, Leverkusen, Germany. Other chemicals are commercially available chemicals (Sigma-Aldrich Chemie GmbH, Taufkirchen, Germany).

Unless nothing else, all data in% the tah relate to mass percent.

Unless nothing else, all analytical measurements relate to a temperature of 23°C.

Specified viscosity determined by means of rotational viscometry in accordance with DIN 53019 at 23°C by using a rotary viscometer of the company Anton Paar Germany GmbH, Ostfildern, Germany.

The content of isocyanate groups define, unless nothing else, volumetric according to DIN-EN ISO 11909.

Specify the particle size determined by laser correlation spectroscopy (instrument: Malvern Zetasizer 1000, Malver Inst. Limited).

The solids content is determined by heating a weighed sample to a temperature of 100°C. At a constant mass calculated solids content by weighing the sample.

The control of free isocyanate groups is realized by means of IR spectroscopy (band at 2260 cm-1).

Example B1)

according to the application for the European patent A-1311571 B1 (blocked by dimethylpyrazolo N 3300 in a mixture of methoxypropylacetate/SN100)

Accordingly experience B1 of a European patent application A-1311571 625 g of Desmodur®N 3300, 104 g of 1-methoxypropylacetate and 209 g of Solventnaphtha®(Shell) is heated to a temperature of 50°C. To the solution was added 314 g of 3,5-dimethylpyrazole so that the temperature did not exceed 65°C. Then stirred at a temperature of 50°C to until nick is such isocyanate groups are no longer detect (approximately one hour). The viscosity of the solution is 3910 MPa·s (23°C, shear rate 186-1).

Example B2)

(same as 1) (blocked by dimethylpyrazolo N 3300, without solvent)

625 g of Desmodur®N 3300 hardware with stirring is heated to a temperature of 50°C. Then add 314 g of 3,5-dimethylpyrazole so that the temperature did not exceed 65°C. then stirred at a temperature of 65°C to until by IR spectroscopy't find any more isocyanate groups (approximately one hour). The mixture became very viscous. When cooled to room temperature't find any fluidity, also after heating to a temperature of 50°C can be no dosing.

This blocked polyisocyanate is unsuitable for obtaining self-curing polyurethane dispersions, as dosing is not possible. The receipt, free of co-solvent dispersions known from the prior art by, therefore, is impossible, because simply refuse to co-solvent.

Example B3)

(experience in relation to the introduction of Diisopropylamine as a blocking means, respectively, method B1 of a European patent application 1311571 B1)

Follow the procedure as described in example 1), but instead of 314 g of 3,5-dimethylpyrazole add 324,3 g disap is operamini.

The viscosity of the solution immediately after cooking is 49300 MPa·s (23°C, shear rate 186-1). For several days in a vessel formed crystals, yield no longer find.

Due to the high viscosity and tendency to crystallization impossible to get a self-curing polyurethane dispersion with the locked diisopropylamino isocyanate groups by analogy with the locked dimethylpyrazolo systems according to the application for the European patent A-1311571.

Example 1)

(not according to the invention; obtaining a dispersion according to the application for the European patent A-1311571 D7)

In the apparatus with a mixing capacity of 2 liters enter 234,8 g complex polyester content of hydroxyl groups of 3.3% and an acid number of about 3 mg KOH/g, consisting of 39.7 percent neopentyl glycol, 6.4% of trimethylpropane, 43.5% of anhydride tetrahydrophthalic acid and 10.4% of adipic acid, and 234,8 g complex polyester content of hydroxyl groups of 2.0% and an acid number of about 1 mg KOH/g, consisting of 30.4% of hexandiol to 1.6, 16.9% of neopentyl glycol and 52.7% of adipic acid, and together with 31,5 g dimethylolpropionic acid, 28,95 g of trimethylolpropane, 69,86 g of N-methylpyrrolidone and 0.80 g of dictate tin is heated to a temperature of 130°C and homogenized for 30 minutes under stirring. Then ohlajdauche temperature of 90°C and with vigorous stirring, with 99.4 g of isophoronediisocyanate (IPDI). Immediately after this, the mixture is heated to a temperature of 130°C and at this temperature withstand up to until by IR spectroscopy't find any more isocyanate groups.

The mixture is then cooled to a temperature of 70°C and mixed with 200,2 g of the solution of the blocked MDI of example B1). After 30 minutes add to 20.9 g of N,N-dimethylethanolamine, stirred for 10 minutes at 70°C and then mixed with 665 g of deionized water.

The dispersion has the following properties:

the solids content49,6%
pH7,7
viscosity (23°C, shear rate 186-1)343 MPa·s
particle size (laser correlation spectroscopy)73 nm

Example 2)

(not according to the invention; following the method of example 1; blocked by dimethylpyrazolo self-curing dispersion, free of co-solvent; blocking in situ implementation stage blokirovka when using catalysis, as described in the application for a European patent A-2006/005878)

In equipment with moving ywaniem 2 litre capacity enter 234,8 g complex polyester content of hydroxyl groups of 3.3% and an acid number of about 3 mg KOH/g, consisting of 39.7 percent neopentyl glycol, 6.4% of trimethylpropane, 43.5% of anhydride tetrahydrophthalic acid and 10.4% of adipic acid, and 234,8 g complex polyester content of hydroxyl groups of 2.0% and an acid number of about 1 mg KOH/g, consisting of 30.4% of hexandiol to 1.6, 16.9% of neopentyl glycol and 52.7% of adipic acid, and together with 31,5 g dimethylolpropionic acid and 28,95 g of trimethylolpropane are heated to a temperature of 130°C and homogenized for 30 minutes under stirring. Then cooled to a temperature of 90°C and with vigorous stirring, with 99.4 g of isophoronediisocyanate (IPDI). Immediately after this, the mixture is heated to a temperature of 130°C and at this temperature withstand up to until by IR spectroscopy't find any more isocyanate groups.

The mixture is then cooled to a temperature of 70°C, then add 140 g of acetone and cooled to a temperature of 40°C. At 40°C add a 50.5 g of 3,5-dimethylpyrazole and 0.8 g of dictate tin, additionally stirred for 20 minutes and then for one hour add 102,4 g of Desmodur® N 3300, with the temperature maintained within the range from 35°C to 40°C. Additionally stirred for one hour, until by IR spectroscopy no longer find any isocyanate groups. After this type of 20.9 g of N,N-dimethylethanol is on, stirred for 10 minutes at 40°C and then mixed with 789 g of deionized water. Not formed any variance, and immediately falls coarse-grained bottom sediment. Further dilution with 363 g of water also does not lead to any dispersion.

Example D3)

(according to the invention; following the method of example 2); blocked by dimethylpyrazolo self-curing dispersion, free from co-solvent, however, getting exercise, with the addition of catalyst to the formation containing hydroxyl groups polyurethane)

In the apparatus with a mixing capacity of 2 liters enter 234,8 g complex polyester content of hydroxyl groups of 3.3% and an acid number of about 3 mg KOH/g, consisting of 39.7 percent neopentyl glycol, 6.4% of trimethylpropane, 43.5% of anhydride tetrahydrophthalic acid and 10.4% of adipic acid, and 234,8 g complex polyester content of hydroxyl groups of 2.0% and an acid number of about 1 mg KOH/g, consisting of 30.4% of hexandiol to 1.6, 16.9% of neopentyl glycol and 52.7% of adipic acid, and together with 31,5 g dimethylolpropionic acid, 28,95 g of trimethylolpropane and 0.8 g of dictate tin is heated to a temperature of 130°C and homogenized for 30 minutes under stirring. Then cooled to a temperature of 90°C and with vigorous stirring, with 99.4 g of isophoronediisocyanate (IPDI). Nepo is directly immediately after this, the mixture is heated to a temperature of 130°C and at this temperature withstand as long while by IR spectroscopy't find any more isocyanate groups.

The mixture is then cooled to a temperature of 70°C, then add 140 g of acetone and cooled to a temperature of 40°C. At 40°C add a 50.5 g of 3,5-dimethylpyrazole additionally stirred for 20 minutes and then for one hour add 102,4 g of Desmodur® N 3300, with the temperature maintained within the range from 35°C to 40°C. Additionally stirred for one hour, until by IR spectroscopy no longer find any isocyanate groups. After this type of 20.9 g of N,N-dimethylethanolamine, stirred for 10 minutes at 40°C and then mixed with 789 g of deionized water. Form a dispersion of minute particles, from which the acetone is distilled off at 40°C under vacuum (120 mbar) for about two hours.

The dispersion has the following properties:

the solids content49,0%
pH8,0
viscosity (23°C, shear rate 186-1)977 MPa·s
particle size (laser correlation spectroscopy)13 nm

Example D4)

(according to the invention; following the procedure of example 3, but using other blocking tools: blocked by butanonoxime self-curing dispersion, free of co-solvent)

In the apparatus with a mixing capacity of 2 liters enter 234,8 g complex polyester content of hydroxyl groups of 3.3% and an acid number of about 3 mg KOH/g, consisting of 39.7 percent neopentyl glycol, 6.4% of trimethylpropane, 43.5% of anhydride tetrahydrophthalic acid and 10.4% of adipic acid, and 234,8 g complex polyester content of hydroxyl groups of 2.0% and an acid number of about 1 mg KOH/g, consisting of 30.4% of hexandiol to 1.6, 16.9% of neopentyl glycol and 52.7% of adipic acid, and together with 31,5 g dimethylolpropionic acid, 28,95 g of trimethylolpropane and 0.8 g of dictate tin is heated to a temperature of 130°C and homogenized for 30 minutes under stirring. Then cooled to a temperature of 90°C and with vigorous stirring, with 99.4 g of isophoronediisocyanate (IPDI). Immediately after this, the mixture is heated to a temperature of 130°C and at this temperature withstand up to until by IR spectroscopy't find any more isocyanate groups.

The mixture is then cooled to a temperature of 70°C, then add 140 g of acetone and cooled to a temperature of 40°C. At a temperature of 40 the C type of 45.7 g butanonoxime, additionally stirred for 20 minutes and then for one hour add 102,4 g Desmodur®N 3300, with the temperature maintained within the range from 35°C to 40°C. Additionally stirred for one hour, until by IR spectroscopy no longer find any isocyanate groups. After this type of 20.9 g of N,N-dimethylethanolamine, stirred for 10 minutes at 40°C and then mixed with 975 g of deionized water. Form a dispersion of minute particles, from which the acetone is distilled off at 40°C under vacuum (120 mbar) for about two hours.

The dispersion has the following properties:

the solids content43,9%
pH8,1
viscosity (23°C, shear rate 186-1)387 MPa·s
particle size (laser correlation spectroscopy)111 nm

Example D5)

(according to the invention, following the method of example 3, but using other blocking tools: blocked by diisopropylamino self-curing dispersion, free of co-solvent)

In the parature with stirring with a capacity of 2 liters enter 234,8 g complex polyester content of hydroxyl groups of 3.3% and an acid number of about 3 mg KOH/g, consisting of 39.7 percent neopentyl glycol, 6.4% of trimethylpropane, 43.5% of anhydride tetrahydrophthalic acid and 10.4% of adipic acid, and 234,8 g complex polyester content of hydroxyl groups of 2.0% and an acid number of about 1 mg KOH/g, consisting of 30.4% of hexandiol to 1.6, 16.9% of neopentyl glycol and 52.7% of adipic acid, and together with 31,5 g dimethylolpropionic acid, 28,95 g of trimethylolpropane and 0.8 g of dictate tin is heated to a temperature of 130°C and homogenized for 30 minutes under stirring. Then cooled to a temperature of 90°C and with vigorous stirring, with 99.4 g of isophoronediisocyanate (IPDI). Immediately after this, the mixture is heated to a temperature of 130°C and at this temperature withstand up to until by IR spectroscopy't find any more isocyanate groups.

The mixture is then cooled to a temperature of 70°C, then add 140 g of acetone and cooled to a temperature of 40°C. At 40°C type of 45.7 g of Diisopropylamine additionally stirred for 20 minutes and then for one hour add 102,4 g Desmodur®N 3300, with the temperature maintained within the range from 35°C to 40°C. Additionally stirred for one hour, until by IR spectroscopy no longer find any isocyanate groups. After this type of 20.9 g of N,N-demethylate is alumina, stirred for 10 minutes at 40°C and then mixed with 975 g of deionized water. Form a dispersion of minute particles, from which the acetone is distilled off at 40°C under vacuum (120 mbar) for about two hours.

The dispersion has the following properties:

the solids content48,9%
pH8,2
viscosity (23°C, shear rate 186-1)1650 MPa·s
particle size (laser correlation spectroscopy)113 nm

Properties in relation to the technical feasibility of proposed according to the invention dispersions follow from table 1.

Get transparent varnish of the following composition. Of transparent varnishes get film, dried for 10 minutes at room temperature and then subjected to a hot dryer for 30 minutes at a temperature of 140°C, respectively 160°C. the resulting films evaluated from the point of view of technical feasibility.

Determination of hardness by pendulum device carried out according to the method of Koenig respectively DIN 53157.

Razmazannosti solvents appreciate later is respectively 1 minute after the time of exposure to the solvent, the sequence of solvents: xylene/methoxypropylacetate/ethyl acetate/acetone. Rating: from 0, very good, to 5, very bad.

Table 1
The dispersion from example No.1 (comparison)D2D3D4
The sample variance [g]150,0150,0150,0150,0
Additol XW 395 [g]1,21,21,21,2
N,N-dimethylethanolamine, 10%in water [g]1,80,7--
Distilled water [g]to 12.0of 17.05,015,0
In General, [g]165,0168,9156,2to 166.2
Solid [%] 45,143,542,244,1
PH8,38,38,38,3
The expiration time of the ISO-Cup, 5 mm [with]37413040
Condition hot drying: 10 minutes at room temperature 30 minutes at a temperature of 140°C
Hardness by pendulum device [with]21201418
Razmazannosti solvents: 1 minute (0-5)4444444444444444
The appearance of the varnish film(1)B. I.B. I.B. I.B. I.
Condition hot drying: 10 minutes at room temp is the temperature +30 minutes at a temperature of 160°C
Hardness by pendulum device [with]21201816
Razmazannosti solvents: 1 minute (0-5)4444444444444444
The appearance of the varnish film(1)B. I.B. I.B. I.B. I.
(1)B. I.=without blemish, faultless

Received on proposed according to the invention the method of dispersion meet the desired requirements of film formation, and values of razmazannosti solvents, respectively, the hardness of the pendulum device hardened films are flawless. Disadvantages compared with solvent-based dispersion according to comparative example 1 in the case of proposed according to the invention dispersions not.

1. A method of obtaining self-curing aqueous polyurethane dispersions, including the following one hundred the AI:
I. introduction in interaction
a1) MDI
with a mixture of
A2) 2,2-bis(hydroxymethyl)alkenylboronic acid as containing reactive towards isocyanate group, anionic hydrophilizing tools and
A3) at least one polyol as one component with the average HE-functionality >1,
either a mixture of A2) and A3), component a1)
K) contains at least one catalyst selected from the group consisting of tertiary amines, compounds of tin, zinc or bismuth;
II. getting IT functional and not containing NCO-groups of the polyurethane with stage I, which is then
III. A4) is mixed with a reactive blocking agent for isocyanate groups selected from the group consisting of butanonoxime, Diisopropylamine or tert-butylbenzylamine, 3,5-dimethylpyrazole, triazole, respectively, and their mixtures;
IV. subsequent introduction into the interaction of this mixture with stage III A5) one or more polyisocyanates selected from group a1), and these polyisocyanates are the same as or different from a1), and then
V. obtaining physical mixture of HE-functional, not containing NCO-groups of the polyurethane and blocked MDI with stage IV, then then either
VI. acid group, HE-functional polyurethane A6) fully or partially de is rotavirus by adding a neutralizing means
VII. and received at this stage VI polyurethane is dispersed in water, or stage VII is carried out until the stage VI.

2. The method according to claim 1, characterized in that stage VI is carried out until the stage VII.

3. The method according to claim 1, characterized in that stage VII is carried out until the stage VI.

4. The method according to claim 1, characterized in that as a catalyst to) use diktat tin.

5. The method according to claim 1, characterized in that as containing reactive towards isocyanate group of the anionic hydrophilizing means A2) using 2,2-dimethylolpropionic acid.

6. The method according to claim 1, characterized in that the blocking means according to stage III use of compounds selected from the group consisting of butanonoxime, Diisopropylamine and 3.5-dimethylpyrazole.

7. The method according to any one of claims 1 to 6, characterized in that after stage II or stage III use up to 30 wt.% in terms of the polyurethane with stage II solvent or mixture of solvents selected from the group consisting of acetone, methyl ethyl ketone and tetrahydrofuran, and mixtures thereof, which is then removed after phase VII by distillation.

8. The use of self-curing aqueous polyurethane dispersion obtained according to the method according to any one of claims 1 to 7, to receive funds to cover.

9. The means for covering, including self-curing is one polyurethane dispersion, obtained according to the method according to any one of claims 1 to 7.

10. Means for coating according to claim 9, selected from the group consisting of paints, varnishes and adhesives.

11. Method of coating substrates, characterized in that used vehicle for a coating according to claim 9 and/or 10.

12. The method according to claim 11, characterized in that car bodies or parts of vehicle bodies are coated using funds to cover according to claim 9 and/or 10.

13. A substrate containing a coating comprising a means for coating according to claim 9 or 10.

14. The substrate according to item 13, wherein the substrate is a fully a vehicle body or part of the body of the car.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing coating material. Disclosed is a method of producing coating material in form of powdered lacquer or a fluid resin, characterised by that one or more alcohols or polyols react with one or more silanes selected from a group consisting of (isocyanatomethyl)methyl-dimethoxysilane, 3-isocyanatopropyl-trimethoxysilane and 3-isocyanatopropyl-triethoxysilane, to form a covalent bond between the alcohol or polyol and the silane such that the reaction product is a high-molecular weight silane which is cured directly using a catalyst, wherein all alcohol or polyol organic functional groups participate in the reaction with the silane organic functional group. Coating material and use thereof are also disclosed.

EFFECT: disclosed method enables to obtain coating material which can be used to make scratch-resistant coatings.

12 cl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to rocket engineering, particularly to production of a protective-adhesive lacquer which is used as a primer for binding an inhibiting coating with the surface of the charge when inhibiting solid-propellant charge. The protective-adhesive lacquer contains 4,4',4"-triphenylmethane triisocyanate, dichloroethane, as an adhesive additive - a product of polycondensation of ethylene glycol, adipic acid and glycerine, with content of hydroxyl groups from 2.00 to 2.30 wt % and dibutyltin dilaurate as a curing agent.

EFFECT: obtaining lacquer with high capacity for protection from migration processes in the "fuel-inhibiting coating" system, which reduces smoke formation, increases adhesion strength between the inhibiting coating and the surface of the propellant charge, which contains polyformaldehyde derivative-based components, avoids use of an additional cellulose acetate-based primer, which ensures strong adhesion of solid-propellant charge pellets with the inhibiting coating for the guaranteed storage life of the charge and which enables to use readily available domestic raw materials.

1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to polymeric heat-reflecting coating compositions which are applied on inflatable structures, protective and rescue equipment (airstairs for civil aviation, floatation rafts, airships, pneumatic tents, heat-reflecting screens, shields for firefighters), consisting of airtight elastic material based on fabric (capron, nylon, lavsan, high-strength aramid fibre SVM). The polymeric heat-reflecting coating composition contains urethane rubber, a hardener, aluminium paste and ethyl acetate.

EFFECT: production of cold-curable polymeric heat-reflecting coating composition, having high resistance to thermal radiation (up to 29 kW/m2) and minimum weight gain (thickness).

3 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to thermally solidificated covering substances based on aprotic solvents. Claimed is covering substance, which contains at least one compound (A), which contains hydroxyl groups, at least one compound (B) with free and/or blocked isocyanate groups, and at least one catalyst (D) for cross-linking silane groups, with one (i) or several components of covering substance containing hydrolysed silane groups and (ii) covering substance can be finally solidificated for covering, which has statistically distributed regions of lattice Si-O-Si. Obtained from covering substance solidificated coating has index of further cross-linking (PCI) lower than 2, with index of the further linking (PCI) being determined as coefficient from memory module E'(200) of finally solidificated coating, measured at 200°C, to minimum of memory module E'(min) of finally solidificated covering, measured at temperature higher than temperature of transition into glass-like state of Tg, and memory modules E'(200) and E'(min),as well as temperature of transition into glass-like state Tg are measured on free films with thickness of layer 40 mcm+/-10 mcm by means of dynamic mechanical thermal analysis (=DMTA) at rate of heating 2 K per minute and frequency 1 Hz and DMTA measurement on free films with thickness of layer 40 mcm+/-10 mcm, which are solidificated for 20 minutes at object temperature 140°C and after solidifying are kept for 8 days at 25°C, before carrying out DMTA measurements. Polyisocyanate (B) at least partially has one or several similar or different structural units of formula -X-Si-R"XG3-X, where G = identical or different hydrolysed groups, in particular alcoxy group, X=organic residue with from 1 to 20 carbon atoms, R" =alkyl, cycloalkyl, aryl or aralkyl, and carbon chain can be broken by non-adjacent oxygen groups, sulphur or NRa, with Ra=alkyl, cycloalkyl, aryl or aralkyl, x=0 to 2. Catalyst (D) is phosphorus-containing, and covering substance contains catalyst (D) from 0.1 to 10 wt % in terms of non-volatile components of covering substance. Also claimed are multi-step method of applying coating with application of claimed covering substance, as well as application of claimed method and versions of claimed coating application.

EFFECT: possibility to obtain transparent varnish coating with high resistance to atmospheric impact.

18 cl, 4 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to thermally solidificated covering substances based on aprotic solvent. Claimed is covering substance, which contains at least one compound (A), containing hydroxyl groups, at least one compound (B), containing isocyanate groups, and at least one phosphorus-containing catalyst (D) for cross-linking silane groups, with one or several components of covering substance containing between 2.5 and 97.5 mole %, counted for totality of structural units -N(X-SiR"x(OR')3-x)n(X'-SiR"y(OR')3-y)m (II) and -Z-(X-SiR"x(OR')3-x) (III), at least one structural unit of formula (II), where R'=hydrogen, alkyl or cycloalkyl, carbon chain can be interrupted by means of non-adjacent groups of oxygen, sulphur or NRa, with Ra= alkyl, cycloalkyl, aryl or aralkyl, X,X'=linear and/or branched alkylene pr cycloalkylene residue with from 1 to 20 carbon atoms, R" =alkyl, cycloalkyl, aryl or aralkyl, and carbon chain can be interrupted by means of non-adjacent groups of oxygen, sulphur or NRa, with Ra= alkyl, cycloalkyl, aryl or aralkyl, preferably R"=alkyl residue, n=0 to 2, m=0 to 2, m+n=2, x,y=0 to 2; and between 2.5 and 97.5 mole %, counted per totality of structural units (II) and (III), at least one structural unit of formula (III), where Z=-NH-, -NR-, -O-, R=alkyl, cycloalkyl, aryl or aralkyl, and carbon chain can be interrupted by means of non-adjacent groups of oxygen, sulphur or NRa, with Ra= alkyl, cycloalkyl, aryl or aralkyl, x=0 to 2, and X, R', R" have value, given above, and covering substance can be finally solidificated before covering, which has statistically distributed regions of lattice Si-O-Si. Also claimed are multi-step method of applying coating with application of claimed covering substance, as well as application of claimed method and versions of claimed coating application.

EFFECT: possibility to obtain transparent varnish coating with high resistance to formation of cracks under atmospheric impact and perfect resistance to scratching.

18 cl, 4 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to thermally solidificated covering substances based on aprotic solvent. Claimed is covering substance, which contains at least one compound (A), containing hydroxyl groups, and at least one compound (B), containing isocyanate groups, and one or several components of covering substance have between 2.5 and 97.5 mole % counted per totality of structural units (I) and (II), at least one structural unit of formula (I), where R'=hydrogen, alkyl or cycloalkyl, and carbon chain can be interrupted by non-adjacent groups of oxygen, sulphur or NRa, with Ra= alkyl, cycloalkyl, aryl or aralkyl, X,X'=linear and/or branched alkylene or cycloalkylene residue with from 1 to 20 carbon atoms; R"= alkyl, cycloalkyl, aryl or aralkyl, and carbon chain can be interrupted by non-adjacent groups of oxygen, sulphur or NRa, with Ra= alkyl, cycloalkyl, aryl or aralkyl, n=0 to 2, m=0 to 2, m+n=2, x,y=0 to 2; and between 2.5 and 97.5 mole % counted per totality of structural units (I) and (II), at least one structural unit of formula (II), where Z=-NH-, -NR-, -O-; R=hydrogen, alkyl, cycloalkyl, aryl or aralkyl and carbon chain can be interrupted by non-adjacent groups of oxygen, sulphur or NRa, with Ra= alkyl, cycloalkyl, aryl or aralkyl, x=0 to 2, and X, R', R" have value, given above; and polyol (A) contains at least one poly(meth)acrylate polyol. Also claimed are multi-step method of applying coating with application of said covering substance, method application and versions of coating application.

EFFECT: possibility of simple obtaining of transparent varnish coatings with high resistance to crack formation under atmospheric impact and perfect resistance to scratching, which do not cause any ecological problems.

15 cl, 2 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: polyurethane coating is made from a composition which contains refined castor oil, an ester, an antifoaming additive BYK-066 based on fluorine-modified polysiloxanes, aluminium oxide, titanium oxide, aerosil, a water adsorbent, an additive BYK-410 - urea in an organic solvent N-methylpyrrolidone, a curing agent isocyanate SUPRASEK 5025, which is 4,4'-diphenylmethane diisocyanate and additionally as filler - dolomite or zeolite or a mixture of dolomite and zeolite in ratio 3.25:1.

EFFECT: coating has high breaking strength and modulus of elasticity in tension, while providing sufficiently high deformation characteristics, particularly tensile elongation.

2 tbl

FIELD: construction.

SUBSTANCE: method to manufacture a coating includes preparation of a mixture by means of mixing of a filler from rubber crumb and a binder based on polyurethane. Simultaneously and separately from each other mixtures are produced for basic and upper layers, at the same time in the mixture for the basic layer they use a filler from rubber crumb with fraction of 2-12 mm, and in the mixture for the upper layer they use a filler from rubber crumb with fraction of 1-3 mm and a pigment dye. In process of mixture mixing for its upper layer it is compacted, afterwards the mixture for the upper layer is serially discharged into a die mould, then the mixture for the basic layer is discharged, and pressed under pressure with the help of a press, then maintained until full hardening, and the produced coating is discharged from the die mould.

EFFECT: high efficiency of coating manufacturing, higher reliability and durability of a coating, possibility to manufacture a double-layer coating with damping properties.

8 cl

FIELD: chemistry.

SUBSTANCE: formulation composition contains: A) 5-95 wt % at least one radiation-curable resin, B) 5-25 wt % silicic acid, C) 0.1-10 wt % at least one adhesion promoter, D) 5-90 wt % at least one radiation-curable reactive diluent, E) 0.5-5 wt % at least one dispersant. The adhesion promoter is selected form phosphoric acid and/or phosphonic acid and/or products of reaction thereof with functionalised acrylates. The composition can additionally contain photoinitiators, pigments and additives, selected from diffusion promoting agents, delustering agents and degassing agents. The compositions are used as a primer, an intermediate layer, coating varnish and/or clear varnish, as well as for making coatings via a coil coating technique.

EFFECT: coatings have flexibility, thereby providing excellent protection of metal substrates from corrosion.

18 cl, 2 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a self-crosslinking binder for coating compositions containing an aqueously dispersed polymer component A having at least one carbonyl group of the ketone or aldehyde type per molecule, and a component B having at least two hydrazine or hydrazide groups per molecule, and at least one structural unit -NR1-NR2-CHR3-CHR4-NH-R5 (I), where the radicals R1, R2, R3 and R4 are each individually selected from a group consisting of a hydrogen radical and a linear or branched alkyl radical having from 1 to 10 carbon atoms, R3 and R4 may additionally be selected from a group consisting of aryl and alkylaryl radicals having from 6 to 15 carbon atoms, and from oxyalkyl radicals with 1 to 10 carbon atoms, where oxy groups may be inserted into the alkyl chain or at the end of an alkyl chain, and R5 is selected from a group consisting of a hydrogen radical, alkyl radicals which may be linear, branched or cyclic and may have from 1 to 10 carbon atoms, and residues of formula -(CH2)n-CO-O-X, where n is an integer of from 1 to 6, and X is a residue of a polyatomic alcohol or phenol. A method of producing such a binder is also described.

EFFECT: producing a coating binder which is self-crosslinking when drying, having fast drying properties and improved chemical resistance and weather resistance.

17 cl, 5 ex, 5 tbl

Adhesive substances // 2466149

FIELD: chemistry.

SUBSTANCE: invention relates to aqueous compositions for gluing substrates, a method of obtaining such compositions, as well as a method of making latent-reactive coatings, films and powders from said compositions. The aqueous compositions for gluing substrates contain: polymers dispersed in water, having groups capable of reacting with isocyanate, such as urethane groups and urea groups; at least one dispersed solid aliphatic polyisocyanate which is not surface-active, with softening temperature higher than or equal to 40°C; one or more compounds of group (subgroup) 5 and 6 elements, in which the oxidation state of said element is at least +4; and optionally other additives and auxiliary materials.

EFFECT: obtaining novel compositions for gluing substrates and latent-reactive coatings, films and powders based thereon, which are stable during storage and stable with respect to colour.

18 cl, 1 dwg, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to the chemistry of foamed polyurethanes, particularly a polyurethane system for making elastic articles, preferably for medical purposes, for example, orthopaedic articles, technical parameters of which have improved sanitary properties which meet their operating requirements. The present invention can also be used to make polyurethane bandages. The polyurethane system for making articles with improved sanitary properties contains compositions based on a polyol compound A, an isocyanate compound B and a mineral agent C, which is dispersed in polyol compound A. The isocyanate compound B used is prepolymers of methylene diphenyl diisocyanates MDI. The mineral agent C used is a mixture of bentonite nanopowders which are intercalated with silver ions Ag+ and cerium ions Ce3+.

EFFECT: improved sanitary properties of the obtained elastic articles, with regard to both inhibiting growth of microorganisms and reducing gas release of volatile toxic organic compounds.

9 cl, 2 dwg, 5 ex

FIELD: textile industry.

SUBSTANCE: fabric is of polyester or polyetheretherketone type. The fabric coating is produced by way of cross-linking anionic aliphatic dispersion with OH-number < 0.5 with hydrophilous aliphatic polyisocyanate, preferably, based on hexamethylenediisocyanate with NCO value 17-18. The fabric may be woven of already coated fibres or filament yarns. The coating is applied on the fabric by way of its contacting with a gluing compound containing a gluing substance activated to perform cross-linking when heated. Then the fabric is ironed at a temperature of 95-100°C. The fabric is pitched on structures at a surface temperature, with the seams and laps not heated over 100°C. The invention excludes the necessity of further application of coating on the fabric after application the coating which ensures application of a significantly less weight in the process of coating.

EFFECT: one eliminates application of any organic solvents in the gluing compounds providing for tension of oil varnishes, liquifiers, fillers or coloured oil varnishes and offers an environmentally safe method for application of coating on an aircraft.

9 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: method involves: (1) reacting a mixture of polyisocyanate and 5-30 wt % mono- or polyisocyanate with a hydrophobic group at 120-180°C in the presence of 0.5-5 wt % carbodiimide catalyst to form a polycarbodiimide containing isocyanate functional groups, with average number of carbodiimide functional groups equal to 1-10, in which the hydrophobic group is an alkyl containing 4-25 carbon atoms which, a fluorinated hydrocarbon, a silicon-containing hydrocarbon or an organosilicon polymer, (2) breaking and/or prolonging the chain from the polycarbodiimide containing isocyanate functional groups by adding a compound in amount of 0.1-1.0 equivalents with respect to content of isocyanate functional groups, where the said compound contains a hydrophilic group and one or more amine and/or hydroxyl functional group simultaneous or subsequent blocking of the remaining isocyanate functional group with a compound containing one or more amine and/or hydroxyl functional groups and, possibly, a hydrophobic group, where the hydrophobic group is an alkyl group containing 4-25 carbon atoms, a fluorinated hydrocarbon, a silicon-containing hydrocarbon or an organosilicon polymer, (3) dispersing the obtained compound in water, and (4) regulating pH of the formed dispersion to a value between 9 and 14 by adding to the obtained dispersion a hydroxide of an alkali metal or a buffer, where the buffer is effective at pH 9-14. The invention also relates to coating mixture containing polycarbodiimide dispersion prepared using the method described above, as well as a curable material obtained by applying said coating mixture onto a substrate.

EFFECT: meeting the requirement for low amount of hydrophilic material needed for dispersing polycarbodiimide, obtaining films or coatings which are less sensitive to water, more resistant to solvents and which have improved properties during attrition testing in wet state, and achieving high cross-link density of the polymer network.

21 cl, 38 ex, 5 tbl

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to mixtures consisting of blocked polyisocyanates designated as hardening agents in monocomponent lacquers of hot drying and comprising: (a) blocked polyisocyanate based on 1,6-diisocyanate hexane; (b) blocked polyisocyanate based on cycloaliphatic diisocyanates chosen from group comprising 1-isocyanato-3,3,5-trimethyl-5-ixocyanatomethylcyclohexane, bis-(4-isocyanatocyclohexyl)methane, 2,6-bis-isocyanatonorbornane, 2,5-bis-isocyanatonorbornane, 1,4-bis-isocyanatomethylcyclohexane and their mixtures, and (c) 3,5-dimethylpyrazole as a single blocking agent of agent of polyisocyanates named in (a) and (b). Blocked polyisocyanates are taken in the weight ratio (a) : (b) = 1:(1.8-2.2). Using mixtures of blocked polyisocyanates provides preparing clear lacquers with good acid resistance, stability against scratching and thermal yellowing.

EFFECT: improved and valuable properties of agents.

1 cl, 6 ex

FIELD: protective coatings.

SUBSTANCE: invention relates to a method for applying onto wood substrate coating with increased resistance to effects of chemical products. Method comprises following stages: (i) addition, to aqueous polyatomic alcohol suspension, of composition based on isocyanate(s) and anionic surfactant having hydrophilic portion containing anionic group and lipophilic portion containing hydrocarbon radical, isocyanate(s)-based composition containing no more than 30% surfactant bound to isocyanate group, to form aqueous emulsion of isocyanate(s) and surfactant; (ii) applying resulting mixture onto wood surface of substrate; and (iii) aging to complete reaction of isocyanate(s) with polyatomic alcohol required to form polyurethane coating.

EFFECT: increased strength of coating (at a level of 90 units) and acquired resistance to a variety of chemical, cosmetic, and woof products according to corresponding standard.

18 cl, 4 dwg, 5 ex

FIELD: rocket technique, chemical technology.

SUBSTANCE: invention relates to a method for preparing a hardening agent for polyurethane compositions based on oligodiene rubbers. Invention describes a method for preparing a hardening agent for polyurethane compositions consisting of the following components, wt.-%: oligodiene urethane prepolymer, 80-91; 20% solution of triphenylmetane triisocyanate in dichloroethane, or 27% solution of triphenylmethane triisocyanate in ethyl acetate, 7-13, and, optionally, transformer oil, 0-10. The process is carried out in the range of temperatures 55-65°C, under residual pressure 1333 Pa for 6 h. Invention provides preparing polyurethane compositions possessing the rupture strength value at the level 38 kgf/cm2, relative elongation 350-600%, elasticity modulus at 50°C at the level 41 kgf/cm2 and adhesion strength to ballistic fuel 41 kgf/cm2. Proposed compositions are able to provide working ability of articles in the range of temperature from -50°C to +50°C.

EFFECT: improved preparing method.

2 tbl, 4 ex

Disperse system // 2204570
The invention relates to one-component dispersion, which has the ability of blending at low (room) temperatures

The invention relates to the production of flexible foams and can be used in the automotive industry, furniture industry, for the production of sports equipment

The invention relates to the field of production of two-component compounds with increased strength and can be used to seal the membrane elements

FIELD: chemistry.

SUBSTANCE: invention relates to polyurethane compositions for producing holographic media which contain (A) one or more polyisocyanates, (B) one or more block copolymers which react with isocyanate, (C) one or more compounds having groups which, during actinic exposure, react with ethylenically unsaturated compounds with polymerisation, (D) optionally one or more free-radical stabilisers and (E) one or more photoinitiators. Topographic media obtained from such polyurethane compositions are also described.

EFFECT: obtaining polyurethane systems having excellent compatibility of the polyurethane polymer matrix with radiation-curable olefinically unsaturated monomers in the composition, and have considerably higher transparency.

13 cl, 3 tbl

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